TWI570160B - Epoxy silicone resin and a hardened resin composition using the same - Google Patents

Description

Epoxy polyoxyn resin and curable resin composition using the same

The present invention relates to an epoxy polyoxyxene resin having a cyclic siloxane coupling, and a thermosetting resin composition having excellent optical properties, hardness, bending property, heat resistance coloring property, and light coloring resistance as essential components thereof. In particular, it relates to a thermosetting resin composition suitable for use in the field of electronic materials and in the field of optical semiconductor materials.

Epoxy resin is mainly used in many fields such as coatings, civil engineering, and electrical appliances because of its excellent electrical properties, bonding properties, heat resistance, etc., especially phenol A diglycidyl ether and bisphenol F diglycidyl ether. An aromatic epoxy resin such as a phenol novolak type epoxy resin or a cresol novolac type epoxy resin is widely used for excellent water resistance, bonding property, mechanical properties, heat resistance, electrical insulation properties, economy, and the like. Used to combine various hardeners. However, since these resins contain an aromatic ring, they are easily deteriorated by ultraviolet rays or the like, and thus are limited in use in fields requiring weather resistance and light resistance.

The epoxy resin composition has a high hardness and therefore has excellent handleability, and can be used for low-output white LED sealing applications, so it is mostly used for low output applications. However, in a high-output LED, it is easy to change color due to an increase in the amount of light emitted and the amount of heat generated, so that it is difficult to obtain a sufficient life. In order to prevent discoloration due to increased heat generation, an epoxy resin having a higher glass transition temperature is used, but the bending property of the strength, flexibility, and the like of the epoxy resin having high elasticity is higher than that of a general epoxy tree. Since the fat is low, there is a problem that the sealing material is easily broken in an environment where the cutting and the like are cut and the temperature is changed drastically. Further, in recent years, the wavelength of the light emitted from the LED is shortened, so that discoloration occurs during continuous use, and the light-emitting output is easily lowered. Therefore, the sealing material needs to have mechanical strength while improving heat resistance coloring resistance and light resistance.

In recent years, we have been developing LED sealing materials based on polyoxyxylene resins with excellent heat resistance and light yellowing resistance, and resin compositions which have been subjected to addition reaction of hydroquinone and alkenyl groups, and hardeners. A report of a resin composition obtained by hardening a polyoxyxylene resin having an epoxy group.

Further, the polyoxyxene resin and the epoxy resin having a polyfluorene skeleton in the main chain mostly have high mobility from the polyfluorene skeleton, but the disadvantage is that the hardness of the cured product is low, the surface is sticky and the strength is low. Therefore, the transparency is deteriorated due to adhesion of dust or the like, and it is difficult to handle the LED, and the manufacturing method, structure, design, and use are limited. Further, although a resin containing a polyphenylene skeleton having a high hardness of a phenyl group can improve handling properties, it has disadvantages such as strength, flexibility, and breakage due to a severe temperature change at the time of switching lamps. Even if the resin having a lower epoxy equivalent of epoxycyclohexyl group can improve the handleability such as surface hardness, the advantages of polyfluorene oxide are impaired, and the requirements of the LED sealing material cannot be withstood, so further improvement is required. Further, the resin composition formed of the polyolefin compound and the organopolyoxane having a hydrofluorenyl group is also required to have improved strength and yellowing.

Moreover, since the number of LEDs mounted on the backlight of the mobile phone and the monitor is large, it is necessary to perform a reflow step of soldering and mounting on the circuit board. Exposing the LED package to the entire lead-free soldering installation according to the environment In the reflow furnace at 260 ° C, the sealing material is colored and broken due to the intense temperature change, and the bonding force between the sealing material and the joint portion is insufficient to be peeled off, and the metal material is broken due to the expansion of the sealing material. Therefore, demand increases the pass rate and productivity.

As described above, even if the polyfluorene resin having excellent weather resistance is used as the substrate, and the physical properties required for the LED sealing material are not obtained, it is required to have sufficient hardness, strength, flexibility, and excellent heat-resistant coloring and UV-resistant coloring. It has the same mass productivity and handleability as epoxy resin.

Patent Document 1 discloses a resin composition derived from an addition reaction of a polyorganosiloxane having a hydroquinone group and a polyorganosiloxane having an alkenyl group. Patent Document 2 discloses a composition of a curable polyorganosiloxane containing a phenyl group, an optical semiconductor element sealing agent using the same, and an optical semiconductor device. Patent Document 3 discloses an epoxy polyoxyxylene resin which is required to have a linear and cyclic siloxane having a branched epoxy group. Patent Document 4 discloses an organopolysiloxane having a diglycidyltrimeric isocyanatoalkyl group at both ends of a main chain and a composition containing the same. Patent Document 5 discloses an addition reaction product of an organic ruthenium compound having two hydrofluorenyl groups and a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and at least one molecule A composition having an addition reaction product of two addition-reactive carbon-carbon double bonds and a compound having a Si-H group. Patent Document 6 discloses an organopolysiloxane having a diglycidyltrimeric isocyanatoalkyl group at both ends of a main chain and a composition containing the same. Patent Documents 7 and 8 disclose an epoxy polyoxyxene resin having an isocyanato ring in the resin and having an epoxy group at the terminal, and a composition containing the same. However, the heat hardening described in the patent documents The above resin composition cannot obtain sufficient characteristics as described above.

Prior technical literature Patent literature

[Patent Document 1] JP-A-2010-248413

[Patent Document 2] JP-A-2010-084118

[Patent Document 3] WO2008/133108

[Patent Document 4] JP-A-2009-275206

[Patent Document 5] JP-A-2008-069210

[Patent Document 6] JP-A-2010-285563

[Patent Document 7] JP-A-2008-274004

[Patent Document 8] WO2007/074813

Summary of invention

An object of the present invention is to provide a cured product having high hardness, excellent heat-resistant coloring property, UV coloring resistance, strength and flexibility, and is suitable for use in the field of electronic materials even in the case of less damage due to reflow and thermal cycling. A thermosetting resin composition for sealing an optical semiconductor. Another object is to provide an epoxy polyoxynoxy resin which is suitable as a material of the above thermosetting resin composition.

The present invention relates to an epoxy polyoxyl resin having an epoxy equivalent (g/eq) of from 200 to 2,000, represented by the general formula (1).

In the formula, R ₁ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. R ₂ represents a divalent hydrocarbon group having 1 to 20 carbon atoms and has 1 to 3 ether-bonding oxygen atoms inside. E ₁ is a monovalent organic residue having at least one epoxy group, and Z is a divalent organic residue. l, m is independently an integer from 0 to 3, and 1≦l+m≦4. n is the number of 0 < n ≦ 100.

In the general formula (1), E ₁ is an organic residue represented by the formula (2).

Z in the general formula (1) is a divalent organic residue represented by the general formula (3), (4) or (22).

In the general formula (3), R ₃ represents a methyl group or a phenyl group, and may be the same or different. k is the number from 0 to 100.

In the general formula (4), R ₄ represents a methyl group or a phenyl group, and may be the same or different. i, j are independently integers from 0 to 3, and 1 ≦ i + j ≦ 4.

In the general formula (22), R ₂₃ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ₂₄ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

Further, in the method for producing an epoxy polyoxyxene resin, the cyclic organosiloxane having SiH at both ends represented by the general formula (5) is contained at both ends of the theoretical amount. Vinyl compound After that, an epoxy resin having at least one epoxy group in one molecule and having one carbon-carbon double bond in one molecule and reacting with an SiH group is used to carry out terminal sealing reaction on the remaining SiH group. A method of manufacturing an epoxy resin.

Wherein R ₁ , l, m are synonymous with the general formula (1).

The above-mentioned compound having a vinyl group at both ends, such as a polyorganosiloxane having a vinyl group at both terminals represented by the general formula (6), (7) or (25) or a trimeric isocyanic acid having a vinyl group at both terminals Things.

Wherein R ₃ and k are synonymous with the general formula (3). R ₄ , i, and j are synonymous with the general formula (4). In the formula (25), R ₂₅ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₂₆ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ₂₇ represents a hydrogen atom or a methyl group.

An epoxy resin reactive with a SiH group such as monoallyl diglycidyl trimer isocyanate.

Further, the present invention is characterized in that the epoxy resin component contains the above epoxy polyoxynoxy resin as a thermosetting resin composition containing an epoxy resin, a curing agent (B) and a curing accelerator (C) as essential components. A thermosetting resin composition. Hereinafter, the above epoxy polyoxyl resin to be added to the thermosetting resin composition is referred to as an epoxy polyoxyl resin (A).

The hardener (B) is, for example, an acid anhydride or a liquid amine compound at room temperature. Further, a hardening accelerator (C) such as a 4-grade ammonium salt or a 4-grade phosphonium salt.

The epoxy resin component preferably contains an epoxy polyoxynoxy resin (A) and a liquid epoxy resin (D) at room temperature, and is added to 100 parts by weight of the epoxy polyoxyl resin (A). 5 to 150 parts by weight of the liquid epoxy resin (D) at room temperature, the epoxy equivalent of the epoxy resin mixture is 180 to 1000.

The thermosetting resin composition may further contain a white pigment (E), and the white pigment (E) is preferably at least selected from the group consisting of cerium oxide, titanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and inorganic hollow particles. 1 species.

Moreover, this invention is an LED device which seals using the said thermosetting resin composition.

Embodiments of the present invention will be described in detail below.

The epoxy polyoxynene resin of the present invention is represented by the above general formula (1), and has an epoxy equivalent of from 200 to 2,000.

In the general formula (1), R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group such as methyl, ethyl, propyl, isopropyl, n-butyl, hexyl, phenyl, naphthyl and the like, but not limited thereto, may be the same or different. The R _{1 is} preferably a methyl group from the viewpoint of physical properties such as heat-resistant colorability and light-resistant coloring property when the cured product obtained by heat treatment is used as the thermosetting resin composition.

In the general formula (1), l and m are each an integer of 0 to 3, and conform to 1≦l+m≦4. In terms of easy availability, the values of l and m are preferably l=1 and m=1. n is an average value (number average), and n represents a number greater than 0 and less than 100. The number of n is preferably 0.05 ≦ n ≦ 30, more preferably 0.05 ≦ n ≦ 20, and particularly preferably 0.1 to 10, from the viewpoints of heat-resistant colorability, light coloring resistance, and mechanical properties when used as a cured product. When the epoxy polyoxyxene resin of the present invention is a mixture of n different molecules, a component in which n is 0 may be present, but a component in which n is 0 is not 100%, and a component in which n is 0 is preferably 0 to 90 wt. %, more preferably 0 to 70% by weight.

In the general formula (1), R ₂ represents a hydrocarbon group having a carbon number of 1 to 20, and may have 1 to 3 ether-bonding oxygen atoms inside. Such structures are, for example, methyl, ethyl, propyl, isopropyl, isopropylidene, butyl, isobutyl, hexyl, xylylene, dodecyl, lower The base or the like represented by the general formula (8) is described, but is not limited thereto. R _{2 is} preferably a C1-6 hydrocarbon group, more preferably a stretching propyl group, as the physical properties of the cured product.

(where h represents the number from 1 to 3).

In the general formula (1), Z represents a divalent organic residue. It is preferably an organic residue containing Si internally or a hydrocarbon group having a carbon number of 1 to 20, and further, the inside of the hydrocarbon group may have 1 to 3 ether-bonding oxygen atoms.

The above divalent hydrocarbon group may have 1 to 3 ether-bonding oxygen atoms in the interior, for example, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, or a general group. The groups represented by the formulae (9) to (16).

In the general formulae (9) to (16), R ₅ is a hydrocarbon group having 1 to 17 carbon atoms. R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ represent a hydrocarbon group having 1 to 20 carbon atoms and may have an oxygen atom inside. X represents a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, a carboxyl group, a sulfonyl group, a sulfinylene group or a single bond.

Z is preferably an organic group containing Si in the inside, and has, for example, an organic group represented by the following general formulas (17) to (21).

In the general formulae (16) to (21), R ₁₂ , R ₁₄ and R _{17 each} represent a hydrocarbon group having a carbon number of 1 to 10 and may have an aromatic ring inside. R ₁₃ , R ₁₆ and R ₁₉ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₁₅ represents a phenyl or a naphthyl group. R ₁₈ represents a hydrocarbon group having a carbon number of 1 to 20, and may have an aromatic ring or an ether-bonded oxygen atom. R ₃ and k are synonymous with the general formula (3), R ₄ , i, j are synonymous with the general formula (4), and R ₂₀ and R ₂₁ represent a divalent hydrocarbon group having 1 to 10 carbon atoms.

However, Z is not limited to these, and two or more types of structures may be added. Among them, Z is preferably a general formula (19) or a general viewpoint from the viewpoints of ease of availability, ease of manufacturability of the epoxy polyoxyxene resin of the present invention, heat-resistant colorability when used as a cured product, light-resistant colorability, and mechanical properties. The structure represented by the formula (20) is more preferably a divalent organic residue represented by the general formula (3), (4) or (22).

In the general formulae (3) and (4), R ₃ and R ₄ independently represent a methyl group or a phenyl group. k is the number from 0 to 100. i, j are independently integers from 0 to 3, and i+j is an integer from 1 to 4. More preferably, in the general formula (3) or (19), R ₃ is a methyl group and 0 ≦ k ≦ 20, and in the general formula (4) or (20), R 4 is a methyl group, i = 1, and j = 1.

In the general formula (22), R ₂₃ represents a hydrocarbon group having 1 to 10 carbon atoms. Such hydrocarbon groups are, for example, methyl, ethyl, propyl, isopropyl, propylene, butyl, isobutyl, hexyl, decyl, etc. Limited to these. R _{23 is} preferably a hydrocarbon group of C1-6, more preferably a propyl group, as the physical properties of the cured product.

In the general formula (22), R ₂₄ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include an alkyl group, an aralkyl group, and an aryl group of a methyl group, an ethyl group, a propyl group, a butyl group, an isopentyl group, a phenyl group, a benzyl group, a tolyl group, a naphthyl group, and the like, but are not limited thereto. Wait. A hydrocarbon group having an aromatic ring such as a phenyl group or a benzyl group is preferred. The material is easily accessible, and R _{4 is} preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a hydrogen atom or a methyl group.

In the general formula (1), E ₁ is a monovalent organic residue having at least one epoxy group, and preferably an epoxytrimeric isocyanate group represented by the formula (2).

The epoxy polyoxyxylene resin of the present invention is produced by the production method of the present invention. The epoxy polyoxyxylene resin of the present invention is produced by reacting a cyclic organosiloxane having SiH at both ends represented by the above general formula (5) with a compound having a vinyl group at both ends of a theoretical amount. Thereafter, an end-sealing reaction is carried out using an epoxy resin having at least one epoxy group in one molecule and having one carbon-carbon double bond in one molecule and having reactivity with the SiH group. In the general formula (5), the same symbols as in the general formula (1) have the same meaning.

The compound having a vinyl group at both ends is preferably a polyorganosiloxane having a vinyl group at both terminals represented by the general formula (6) or the general formula (7), or both ends represented by the general formula (25). A vinyl trimeric isocyanate derivative, but is not limited thereto. The polyorganosiloxane having a vinyl group at both ends represented by the general formula (6) or the general formula (7) is a Z represented by the general formula (3) or the general formula (4), and thus is equivalent to the general formula (3). ) or (4) the same mark has the same meaning. The compound containing a vinyl group at both terminals of Z represented by the above general formulas (9) to (20) can be understood from the above. In the general formula (25), R ₂₅ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₂₆ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ₂₇ represents a hydrogen atom or a methyl group. R ₂₅ corresponds to R _{24 of the} general formula (22).

a trimeric isocyanide containing a vinyl group at both ends represented by the general formula (25) The acid derivative is not particularly limited as long as it is known, and various compounds can be selected. For example, diallyl isocyanuric acid, dimethylallyl isocyanuric acid, monomethyl diallyl isocyanate, monomethyl dimethylallyl isocyanate, monoethyl Diallyl isocyanurate, monoethyl dimethylallyl isocyanate, monopropyl diallyl isocyanate, monopropyl dimethylallyl isocyanate, monoisoamyl Allyl trimeric isocyanate, monoisoamyl dimethylallyl isocyanurate, monophenyl diallyl isocyanate, monophenyl dimethylallyl isocyanate, mononaphthyl diene The propyl trimeric isocyanate, the mononaphthyl dimethyl propylene trimeric isocyanate, and the like are not limited thereto, and two or more kinds may be used in combination if necessary. The preferred structure of the trimeric isocyanic acid derivative compound is diallyl isocyanuric acid, monomethyl diallyl isocyanate, monophenyl diallyl isocyanurate, particularly preferably Diallyl isocyanuric acid, monomethyl diallyl isocyanurate.

Further, the trimeric isocyanic acid derivative containing a vinyl group at the both ends may be used, for example, in the presence of a Lewis acid such as aluminum chloride, iron chloride or activated clay, as described in US Pat. No. 2830051, and If necessary, a method of reacting a triallyl cyanuric acid with a reaction solvent such as xylene with a phenol or the like added thereto to obtain a diallyl cyanuric acid may be further mixed with an alkyl halide. The reaction may be carried out by N-alkylation. Further, as described in Journal of Organic Chemistry vol. 35, No. 7, p. 2253-2257 (1970), an allyl isocyanate and potassium cyanate are obtained by using a non-protic polar solvent such as dimethylformamide. After the reaction, the method of obtaining a diallyl isocyanuric acid by neutralization with an acid, and if necessary, an alkyl group The halide is N-alkylated. Further, as described in Journal of American Chemical Society vol. 51, p. 2221 (1929), after reacting phenyl isocyanate with methyl carbamate to form monophenyltrial isocyanate, and allyl halide The reaction yields monophenyl diallyl isocyanate. However, the present invention is not limited to these, and the present invention can be carried out in a preferred form to obtain a trimeric isocyanate derivative compound having a vinyl group at both terminals.

The production method of the present invention is particularly preferable in that a polyorganosiloxane containing SiH groups at both ends is first introduced into a reaction system, and secondly, an amount of unreacted SiH groups is left in the use, and a compound containing a vinyl group at both ends is sequentially added. After confirming the completion of the reaction, the terminal sealing reaction was carried out using an epoxy resin reactive with SiH groups. The compound having a vinyl group at both ends may be used in an amount of the above epoxy equivalent when the terminal is sealed with an epoxy resin having a double bond, and is not particularly limited, but is terminated when a compound having a vinyl group at both terminals is terminated. Preferably, the SiH group-containing polyorganosiloxane contains 20 to 80% of SiH groups at both ends. Further, for the reason described above, it is preferred to use the general formula (1), E ₁ is an epoxy trimeric isocyanate group represented by the general formula (2), R ₂ is a stretching propyl group, and R ₁ is an A group. The raw materials of the base, m=1, and l=1. Further, it is preferable to use Z as a group represented by the general formula (3), (4) or (22), and R ₃ is a methyl group, 0 ≦ k ≦ 20, and R ₄ in the general formula (7) is A raw material of methyl group, i=1, j=1. Further, two or more kinds of polyorganosiloxanes represented by the general formula (6), the general formula (7) or (25), or a trimeric isocyanic acid derivative having a vinyl group at both terminals may be used in combination.

The epoxy resin having reactivity with the SiH group has at least one epoxy group in one molecule and one SiH group in one molecule. A reactive carbon-carbon double bond. For example, o-allylphenyl glycidyl ether, 2-allyl-4-methylphenyl glycidyl ether, 2-allyl-5-methylphenyl glycidyl ether, 2-allyl Monocyclic epoxy resin such as -6-methylphenyl glycidyl ether and its nuclear hydrogenated epoxy resin; 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl- Olefin containing cyclic structure such as 4-vinylcyclohexene oxide, 4-vinyl-1-hexene-2-oxide, vinyl norbornene monooxide, dicyclopentadiene monooxide An epoxy resin derived from a compound; an epoxy resin containing a hetero atom in a ring structure such as monoallyl diglycidyl trimer isocyanate; and the like, but is not limited thereto. Further, these epoxy resins may be used in combination of two or more kinds. The epoxy resin which is reactive with the SiH group is particularly preferably a monoallyl diglycidyl tripolyisocyanate which can impart an organic residue represented by the general formula (2).

In addition to the above, for example, a reaction is carried out, and a cyclic organic siloxane having SiH groups at both ends, a polyorganosiloxane having a vinyl group at both terminals, and a monoallyl diglycidyl isocyanate are introduced into the reaction system. a hydroquinone alkylation reaction, or a mixture of a carbon-carbon double bond reactive with a SiH group, a polyorganosiloxane having a vinyl group at both ends, and a monoallyl diglycidyl trimer After the isocyanate is introduced into the reaction system, the polyorganosiloxane containing SiH groups at both ends is further subjected to hydroquinone alkylation, and at this time, the copolymerization of the vinyl group is contained at both ends of the monoallyl diglycidyl trimeric isocyanate. The reaction rate of the hydroquinone alkylation reaction of the organic siloxane is obviously faster, so that it is easy to selectively form a decyl alkane resin having no epoxy group in the reaction system. Therefore, the obtained epoxy polyoxyl resin will undergo phase separation and become cloudy. The transparency is lost, and even if it is not cloudy, the effect of the present invention cannot be obtained in terms of the physical properties of the cured product.

The hydroquinone alkyl addition reaction is widely known to be carried out in the presence of a noble metal catalyst. The catalyst used may be any of the various noble metals or complexes thereof known. The noble metal catalyst is, for example, platinum, rhodium, palladium, iridium or iridium, and the like, and may be used in combination of two or more kinds as necessary. Further, these metals may be used for fixing to a particulate carrier material such as carbon, activated carbon, alumina, cerium oxide or the like.

Complexes of noble metals such as platinum halide compounds (PtCl ₄ , H ₂ PtCl ₆ -6H ₂ O, Na ₂ PtCl ₆ -4H ₂ O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum- Alkoxide complex, platinum-ether complex, platinum-carbon ruthenium complex, platinum-ketone complex, platinum-1,3-divinyl-1,1,3,3-tetramethyl Platinum-vinyl oxime complexes such as decane, bis(γ-picoline)-platinum dichloride, tri-methyldipyridine-platinum dichloride, dicyclopentadiene-platinum Chloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis(alkynyl)bis(triphenylphosphine)platinum complex, bis(alkynyl)(cyclooctadiene) The platinum complex, the ruthenium chloride, the tris(triphenylphosphine) ruthenium chloride, the tetraammine-ruthenium chloride complex, and the like are not particularly limited, and two or more kinds may be used as necessary.

The noble metal catalysts may be used alone or in advance in a solvent for dissolution and then used in a reaction system. The ratio of use of the noble metal catalyst is not particularly limited, but the total weight of the raw materials used for the general reaction is from 0.1 ppm to 100,000 ppm, preferably from 1 ppm to 10,000 ppm.

Hydroquinone alkyl addition reaction can be carried out without solvent, but if necessary The reaction system may be diluted with an organic solvent, and it may be one which does not affect the reaction, and is not particularly limited. For example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone Aliphatic ketones; aromatics such as benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, dichlorobenzene; diethylene glycol dimethyl ether, triethylene glycol dimethyl Ethers such as ethers; esters of ethyl acetate, n-butyl acetate, and the like. These organic solvents may be used in the form of a mixture of two or more kinds.

The temperature condition of the hydroquinone alkyl addition reaction is not particularly limited and is usually from 0 ° C to 200 ° C, preferably from 30 ° C to 180 ° C. When the reaction is carried out below 0 ° C, it takes time and is not advantageous for the economic side. When the reaction is carried out at 200 ° C or more, an addition reaction of an epoxy group with a hydroquinone moiety is caused, and it is difficult to control the reaction.

The epoxy polyoxynene resin of the present invention has an epoxy equivalent of from 200 to 2,000. In this range, a cured product having excellent transparency, heat-resistant coloring property, glass transition temperature, and flexibility can be obtained. When the epoxy equivalent is outside this range, the cured product is embrittled, and the surface hardness is low, which is sticky, and it is unfavorable because the heat-resistant coloring property is deteriorated.

Next, the thermosetting resin composition of the present invention will be explained. The thermosetting resin composition contains an epoxy resin, a curing agent (B), and a curing accelerator (C) as essential components, and the epoxy resin component contains the epoxy polyoxynene resin of the present invention. When the thermosetting resin composition is described, the epoxy polyoxynene resin of the present invention is referred to as an epoxy polyoxyl resin (A).

The curing agent (B) contained in the thermosetting resin composition of the present invention may be a known hardening agent for an epoxy resin, and various compounds may be used. example Such as organic amine compounds, dicyandiamide and its derivatives; 2-methylimidazole, 2-ethyl-4-methylimidazole and other imidazoles and their derivatives; bisphenol A, bisphenol F, bromination a divalent phenol compound such as bisphenol A, naphthalene diol or 4,4′-bisphenol; a novolac resin or an aralkyl phenol resin obtained by condensation reaction of phenol or naphthol with formaldehyde or xylene glycol; a polyvalent carboxylic acid obtained by the reaction of an acid anhydride with a polyvalent organic alcohol; succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, bare anhydride, hydrogenated bare anhydride, trimellitic anhydride, pyromelli-4 An acid anhydride or the like; an anion species consisting of a bismuth adipate compound, an organic cation molecule having a sulfonium cation, an iodonium cation, a tetrafluoroborate anion, a hexafluorophosphorus anion, a hexafluoroarsenic anion, and a hexafluoroantimonium anion; The cationic hardening agent formed by the salt compound or the like may be used in combination of two or more kinds as necessary. In the present invention, in particular, in order to obtain transparency, heat-resistant coloring property, and light-resistant coloring property, the curing agent is preferably a liquid amino compound (including an amine-based resin) or an acid anhydride, more preferably hexahydrophthalic anhydride, methylation. Hexahydrophthalic anhydride, hydrogenated bare anhydride.

The hardening accelerator (C) may be a known hardening accelerator for epoxy resins, and various compounds are suitable. For example, an organic metal salt such as a tertiary amine and a salt thereof, an imidazole or a salt thereof, an organic phosphine compound and a salt thereof, zinc octylate or tin octylate may be used in combination of two or more kinds as necessary. In particular, in order to obtain the effects of the present invention, the hardening accelerator is preferably a 4-grade ammonium salt, an organic phosphine compound, or a 4-grade sulfonium salt, and more preferably a catalyst is a 4-grade sulfonium salt.

In the thermosetting resin composition of the present invention, the components (A), (B), and (C) described above are essential components. However, in order to adjust the viscosity, the curing rate, and the like, the manufacturer may use (A) for the purpose of the preferred embodiment. Outside the ingredients An epoxy resin or an epoxy compound having two or more epoxy groups in one molecule and liquid at room temperature is used as the component (D). When the epoxy equivalent (g/eq) in the mixture of (A) and (D) is in the range of from 180 to 1,000, the effects of the present invention can be obtained.

The component (D) is an epoxy resin different from the component (A), and various compounds which are liquid or not at room temperature may be selected, either alone or in combination. For example, an aromatic ring of an epoxy resin derived from a monocyclic divalent phenol such as resorcinol, hydroquinone or 2,5-di-tert-butylhydroquinone is a nuclear hydride; 1,3-naphthenediol An epoxy resin derived from a naphthalene glycol such as 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol or 2,7-naphthalenediol, and an aromatic ring thereof Hydrogenated; 4,4'-isopropylidenediphenol, 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis (2,6-di Methylphenol), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxy-3,3' , 5,5'-tetramethyldiphenylmethane, 4,4'-by-butylene bisphenol, 4,4'-isopropylidene bis(2-tert-butylphenol), 4,4' An epoxy resin derived from a phenol such as cyclohexylidenediol or 4,4'-butylidenebis(6-tert-butyl-2-methyl)phenol, and an aromatic ring-nucleated hydrogenated epoxy Resin, etc.

Further, the component (D) is an alicyclic epoxy resin as exemplified in the following general formulas (31) to (35).

(wherein g and f represent an integer from 1 to 20).

Further, the component (D) is an alicyclic epoxy resin represented by the following general formula (36).

(R ₃₂ SiO _3/2 ) _w (R ₃₃ R ₃₄ SiO) _x (Me ₃ SiO _1/2 ) _y (36) (wherein R ₃₂ to R ₃₄ are each a carbon number which may contain an epoxy group internally) The hydrocarbon group and the aromatic group to 20 may have 1 to 3 etheric oxygen atoms in the interior. However, in R ₃₂ to R ₃₄ , one or more epoxy groups are required. Further, R ₃₃ and R ₃₄ may not contain a ring at the same time. The oxy group, w to y, is in accordance with w+x+y=1, 0≦w<1, 0<x<1, and 0<y<0.75).

The component (D) is not limited to the above epoxy resin, and two or more kinds thereof may be used as necessary.

The epoxy resin component is an epoxy resin (A) as an essential component, and further contains a liquid epoxy resin (D) and other epoxy resins added as necessary. The amount of the epoxy resin (D) to be added is preferably 5 to 150 parts by weight based on 100 parts by weight of the epoxy polyoxyl resin (A), and the epoxy equivalent of the entire epoxy resin component is preferably in the range of 180 to 1,000. Further, the content of the epoxy polyoxyl resin (A) in the epoxy resin component is 40% by weight or more, preferably 60% by weight or more.

When the thermosetting resin composition of the present invention is used for LED sealing applications, it is preferred to add an antioxidant to prevent oxidative deterioration upon heating to obtain a cured product having less coloration.

The antioxidant can be a known compound for various compounds. For example, 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, stearin-β-(3,5-di Monophenols such as -tert-butyl-4,4-hydroxyphenyl)propionate-2,2-extended methylbis(4-methyl-6-tert-butylphenol), 2,2- a bisphenol such as methyl bis(4-ethyl-6-tert-butylphenol) or 4,4'-thiobis(3-methyl-6-tert-butylphenol), 1,1, 3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert Polymeric phenols such as -butyl-4-hydroxybenzyl)benzene, tetrakis(methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] 9,10-Dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydrogen Oxaphosphorus phenanthrene oxidation of -9-oxo-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide Species, 2 lauryl 3,3'-dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-dilauryl 3,3'-thiodipropyl An ester-containing thioether compound such as an acid ester, distearyl 3,3'-dilauryl 3,3'-thiodipropionate or pentaerythritol tetrakis(3-lauryl thiopropionate) Oxidizer. These antioxidants may be used in combination of two or more kinds as necessary.

Further, other thermosetting resins may be added to the thermosetting resin composition of the present invention. Such thermosetting resins such as unsaturated polyester resins, thermosetting acrylic resins, thermosetting amine-based resins, thermosetting melamine resins, thermosetting urea resins, thermosetting urethane resins, and thermosetting The propylene oxide resin, the thermosetting epoxy/propylene oxide composite resin, and the like are not limited thereto.

The curable resin composition of the present invention contains the components (A) to (C) as essential components, but also contains a resin component (including other resins and components which become partial resins after curing. For example, monomers, hardeners, and hardening) The promoter (but not including the solvent or the filler) is preferably 60% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and more preferably the component (A) to the component (B). Further, the addition ratio of the component (A), the component (B) and the component (C) is preferably determined by the following method.

When the component (B) is not a cationic curing agent, the epoxy equivalent of the component (A) and the equivalent of the functional group in the hardener of the component (B) are preferably in the range of 0.8 to 1.5. When it is outside this range, the functional group in the unreacted epoxy group or the curing agent remains after hardening, and the function of forming the hardness and heat resistance of the cured product is not preferable. Moreover, the addition ratio of the component (C) of the hardening accelerator is preferably in the range of 0.1% by weight to 5% by weight based on the total of the components (A) and (B). When it is less than 0.1% by weight, the gelation time is slowed down and the rigidity at the time of hardening is lowered, so that workability is lowered, and vice versa. When it is over 5.0% by weight, it hardens during the forming, and it is easy to be unfilled.

When the component (B) is a cationic hardener, it is 0.01 to 10 parts by weight, preferably 0.1 part by weight to 5 parts by weight, per 100 parts by weight of the component (A). When the amount is less than 0.01 part by weight, the curing failure tends to occur, and when it exceeds 5 parts by weight, it is disadvantageous in terms of heat-resistant coloring property.

When the thermosetting resin composition of the present invention contains (E) a white pigment, it can form a thermosetting resin composition suitable for light reflection.

The white pigment (E) can be selected from various materials for known materials. For example, metal oxides such as cerium oxide, aluminum oxide, magnesium oxide, cerium oxide, titanium oxide, and zirconium oxide, inorganic silicate glass, aluminosilicate glass, borosilicate glass, white sand, etc. It is not limited to these, and if necessary, two or more types can be used together. A preferred white pigment is at least one selected from the group consisting of cerium oxide, titanium oxide, aluminum oxide, magnesium oxide, zirconium oxide and inorganic hollow particles, and alumina and oxidation are preferred from the viewpoints of thermal conductivity and light reflection characteristics. titanium.

The content of the above white pigment (E) is preferably in the range of 10 to 85 vol% based on the total amount of the resin composition. When the content of the white pigment (E) is 10 vol% or less, the whiteness is insufficient to obtain the light reflectivity of the sufficiently cured product. Moreover, when it exceeds 85 vol%, the kneadability and moldability of the resin composition may be deteriorated.

The thermosetting resin composition for light reflection can be used as an additive such as a coupling agent in order to improve the surface bondability with the white pigment (E). a coupling agent having an alkoxy decane or an alkoxy titanate having any one of an epoxy group, an amine group, a thiol group, an acryl group, and a vinyl isocyanate group. For esters, various materials can be selected for known materials. The amount of the additive to be used is not particularly limited, and a preferred amount can be determined by the manufacturer. However, it is generally 5% by weight or less based on the total amount of the resin composition.

When the thermosetting resin of the present invention is used as an electronic member, the use and the production steps thereof are not particularly limited. For example, it can be used as a semiconductor sealing material, and the thermosetting resin composition of the present invention is mixed with a filler such as cerium oxide, and then kneaded by a kneader or a heated three-seat roll to be thinned, and then fed to a sealing mold. The mode of heat hardening in the empty hole. Further, after mixing a liquid hardening agent at room temperature, it is necessary to adjust the viscosity to a desired viscosity by using a filler such as cerium oxide, aluminum oxide or titanium oxide, and then to inject the resin into a predetermined position.

The method of uniformly dispersing and mixing the thermosetting resin composition of the present invention is not particularly limited, and can be carried out by a preferred method. For example, a method of kneading various components using a mixing roll, an extruder, a kneader, a roller, an extruder, a spinning/revolving stirring mixer, and the like, and then cooling the obtained kneaded material and pulverizing it. Further, from the viewpoint of dispersibility at the time of kneading, it is preferred to carry out the temperature at which the resin composition can be treated in a molten state.

The thermosetting resin composition of the present invention can be obtained by a method in which dispersion, mixing, cooling and pulverization are carried out, and the tablet is in a sheet-like transport mode. At this time, the female mold is formed on the lead frame in which the metal wiring is previously formed, and is applicable to the optical semiconductor mounting housing. Further, it is applied and pressure-molded on a copper foil to obtain a white copper sheet laminate. This white copper sheet laminate is suitably used as a circuit board for mounting an optical semiconductor.

When the thermosetting resin composition of the present invention is applied to an electronic member, The use and the production steps are not particularly limited as long as they are known. For example, when it is used as a semiconductor sealing material, the thermosetting resin composition of the present invention is mixed with a filler such as ruthenium dioxide, and then kneaded by a kneader or a heated three-seat roll to be thinned, and then fed to a sealing mold. The mode of heat hardening in the air hole. Further, after mixing a liquid hardening agent at room temperature, if necessary, a filler such as ceria, alumina, or titanium oxide may be used to adjust the desired viscosity, and then the resin may be placed in a predetermined position.

Further, after the substrate of the circuit board, for example, a glass fiber cloth, is impregnated with the thermosetting resin composition of the present invention, the copper foil is bonded by press molding, or the present invention is used by a casting method or the like. A method in which a thermosetting resin composition is applied onto a copper foil and then bonded to a desired substrate.

In addition, it can be used as a primer for sealing and bonding the substrate to the semiconductor. When a liquid hardener is mixed at room temperature, a filler such as cerium oxide, aluminum oxide, titanium oxide or rubber particles is used if necessary. Then adjust to the desired viscosity, and then inject the resin into a certain position.

In addition, the use of the optical member is, for example, an optical lens, a sealing agent for an optical semiconductor, a white molding material for an optical semiconductor, an optical semiconductor bonding agent, etc., but the use thereof is not limited thereto, and a known use and manufacturing procedure are applied. One of the resin compositions for optical members is, for example, a thermosetting resin composition for light reflection, which is obtained by adding a white pigment (E) as described above.

For example, the optical lens material can be fabricated by known steps such as dispensing mode, transport mode mode, and the like.

When it is used as a sealant for an optical semiconductor device (LED device), the optical semiconductor element is connected to an external electrode by a metal wire or the like, and then used for transport. Method of filling with known techniques such as mode mode and bottling method. In this case, in order to convert the light emitted from the optical semiconductor element, the thermosetting resin composition of the present invention can use various known fluorescent powders. Further, in order to find appropriate thixotropy, a known filler such as cerium oxide or Aerosil or a known additive such as a decane coupling agent or a surfactant may be added.

The photo-semiconductor is suitably used for a white molding material, and after mixing the thermosetting resin composition of the present invention with a filler such as ceria, titanium oxide or alumina, it is kneaded by a kneader or a heated three-roller and then exfoliated. A transport mode in which the holes of the sealing mold are thermally hardened.

The bonding agent for an optical semiconductor device is applied, and a thermosetting resin composition of the present invention is kneaded by a roll or the like, and a paste such as ceria, titanium oxide, aluminum oxide or silver powder used as necessary to form a paste, and then dispensed. A method in which a film material is applied to a substrate, a film-like material is bonded to a substrate, and a semiconductor element is thermally cured.

The thermosetting resin composition of the present invention can be applied to a substrate of a Teflon (registered trademark) plate, a PET film, a polyimide or the like in a film form using a spin coater, a bar coater or the like, and after heat curing. The substrate is peeled off to obtain a film.

The thermosetting resin and the thermosetting film obtained by the above method are suitable for various applications such as known electronic component applications and optical member applications, and are applicable to flexible printed wiring boards, anisotropic conductive films, cover films, and die-bonding films. Use of an electronic component such as an interlayer insulating material, a transparent protective film, an optical waveguide film, or an optical semiconductor film.

Example

The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

Example 1

In the general formula (5), R ₁ is a methyl group, l=1, m=1, 33 parts by weight of a cyclic organosiloxane having a SiH group at both ends (SiH group is 0.25 equivalent), and dioxane 120 weight 0.17 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 500 mL separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 10 parts by weight (vinyl group: 0.04 equivalent) of the organic oxirane having a vinyl group at both ends of the general formula (6), R ₂ being a methyl group and k having an average value of 4 was introduced into the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by gel permeation chromatography (GPC), 57 parts by weight of monoallyl diglycidyl trimer isocyanate (0.21 equivalent of vinyl group) was added in one hour to dissolve in 57 parts by weight of dioxane. Solution. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution to confirm that no hydrogen was generated, and the remaining platinum was filtered using diatomaceous earth. catalyst. After the solvent of the filtrate is distilled off using an evaporator, l=1, m=1, n of the general formula (1) have an average value of 0.2, R ₁ is a methyl group, R ₂ is a propyl group, and E ₁ is a general formula ( 2) The substituent represented by Z, is represented by the general formula (3), R ₃ is a methyl group, and the average value of k is 4, and the epoxy group of the trimeric isocyanato ring having an epoxy group at both ends is The epoxy resin (ES1) was 88 parts by weight. The resin had an epoxy equivalent of 235 and a viscosity (25 ° C) of 680 Pa‧s. The IR spectrum of this resin is shown in Figure 1.

Example 2

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends thereof is 33 parts by weight (SiH group is 0.25 equivalent), and dioxane is 150 weight. 0.32 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 500 mL separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 23 parts by weight (vinyl equivalent of 0.1 equivalent) of the organic oxirane having a vinyl group at both ends of the general formula (6), R ₃ being a methyl group and k having an average value of 4 was introduced into the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 44 parts by weight of monoallyl diglycidyl trimeric isocyanate (the vinyl group was 0.16 equivalent) was added in one hour, and the resulting solution was dissolved in 44 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution to confirm that no hydrogen was generated, and the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate was distilled off using an evaporator to obtain l=1, m=1, n of the general formula (1), and the average value of n was 0.7, R ₁ was a methyl group, R ₂ was a propyl group, and E ₁ was a general formula (2). The substituent represented by Z, is represented by the general formula (3), R ₃ is a methyl group, and the average value of k is 4, and the epoxy polycondensation of the trimeric isocyanato ring having an epoxy group at both ends is used. Oxygen resin (ES2) 91 parts by weight. The resin had an epoxy equivalent of 313 and a viscosity of 200 Pa‧s.

Example 3

In the general formula (5), R ₁ is a methyl group, l=1, m=1, 30 parts by weight of a cyclic organic siloxane having a SiH group at both ends (SiH group is 0.22 equivalent), and dioxane 150 weight 0.17 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 500 mL separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, in the general formula (6), R ₃ was a methyl group, and an average value of k was 8 and 26 parts by weight of a vinyl oxirane having a vinyl group (vinyl group of 0.07 equivalent) at both ends was put into the reaction system. After confirming that the molecular weight was stopped increasing by the GPC method, 44 parts by weight of monoallyl diglycidyl trimeric isocyanate (the vinyl group was 0.16 equivalent) was added in one hour, and the resulting solution was dissolved in 44 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution to confirm that no hydrogen was generated, and the remaining platinum was filtered using diatomaceous earth. catalyst. After the solvent of the filtrate is distilled off using an evaporator, l=1, m=1, n of the general formula (1) have an average value of 0.5, R ₁ is a methyl group, R ₂ is a propyl group, and E ₁ is a general formula ( 2) The substituent represented by Z, is represented by the general formula (3), R ₃ is a methyl group, and the average value of k is 8 and both ends have an epoxy group of an epoxy group-containing trimeric isocyanato ring. 91 parts by weight of a silicone resin (ES3). The resin had an epoxy equivalent of 319 and a viscosity of 160 Pa‧ s. The IR spectrum of this resin is shown in Figure 2.

Example 4

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and 134 parts by weight of a cyclic organosiloxane having a SiH group at both ends (SiH group is 1.0 equivalent), and dioxane 350 weight 0.70 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, in the general formula (6), R ₃ was a methyl group, and an average value of k was 4, and 135 parts by weight of a vinyl oxirane having a vinyl group at both ends (vinyl group of 0.56 equivalent) was placed in the reaction system. After confirming that the molecular weight was stopped by the GPC method, 124 parts by weight of monoallyl diglycidyl trimer isocyanate (0.44 equivalent of vinyl group) was added in one hour to dissolve the solution in 124 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 1.3, R ₁ is a methyl group, R ₂ is a propyl group, and E ₁ is a general formula ( 2) The substituent represented by Z, is represented by the general formula (3), R ₃ is a methyl group, and the average value of k is 4, and the epoxy group of the trimeric isocyanato ring having an epoxy group at both ends is The epoxy resin (ES4) was 347 parts by weight. The resin had an epoxy equivalent of 439 and a viscosity of 30 Pa‧s.

Example 5

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends thereof is 21 parts by weight (SiH group is 0.16 equivalent), and dioxane is 100% by weight. 0.17 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 500 mL separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 54 parts by weight (vinyl group: 0.07 equivalent) of an organic siloxane having a vinyl group at both ends of the general formula (6), R ₃ being a methyl group and k having an average value of 18 was introduced into the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 26 parts by weight of monoallyl diglycidyl trimer isocyanate (0.09 equivalent of vinyl group) was added in one hour to dissolve a solution of 26 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.8, R ₁ is a methyl group, R ₂ propyl group, and E ₁ is a general formula (2). The substituent represented by Z, is represented by the general formula (3), R ₃ is a methyl group, and the average value of k is 18, and the epoxy polycondensation of the trimeric isocyanato ring having an epoxy group at both ends is used. Oxygen resin (ES5) 93 parts by weight. The resin had an epoxy equivalent of 541 and a viscosity of 8 Pa‧s. The IR spectrum of the resin is shown in Figure 3.

Example 6

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and 134 parts by weight of a cyclic organosiloxane having a SiH group at both ends (SiH group is 1.0 equivalent), and dioxane 100 weight 0.8 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 1 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 72 parts by weight (vinyl equivalent of 0.45 equivalents) of a cyclic organooxane having a vinyl group at both ends of the general formula (7), R ₄ being a methyl group, i=1, j=1, was put into the reaction in one hour. Department. After confirming that the molecular weight was stopped by the GPC method, 155 parts by weight of monoallyl diglycidyl trimer isocyanate (0.55 equivalent of vinyl group) was added in one hour to dissolve the solution of 155 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.8, R ₁ is a methyl group, R ₂ is a propyl group, and E ₁ is a general formula ( 2) The substituent represented by Z, which is represented by the general formula (4), wherein R ₄ is a methyl group, i=1, and j=1 has an epoxy group containing an epoxy group-containing trimeric isocyanato ring. Polyoxygenated resin (ES6) was 321 parts by weight. The resin had an epoxy equivalent of 325 and was a solid resin having no fluidity at room temperature.

Synthesis Example 1

26.4 parts by weight of the organohydrogenated hydrazine represented by the formula (37) (0.2 equivalent of the SiH group), 78 parts by weight of dioxane, and 0.14 parts by weight of platinum (carbon supported amount of 3%) were placed in a stirring motor and refluxed. The 500 mL separable flask of the cooling tube and the nitrogen line was heated to 100 ° C with stirring. Next, 56.2 parts by weight of a monoallyl diglycidyl cyanurate (0.2 equivalent of a vinyl group) was dissolved in a solution of 56 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction solution was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the occurrence of no hydrogen gas, the residual platinum catalyst was used. The solvent of the filtrate was distilled off using an evaporator to obtain 74 parts by weight of an epoxy polyoxyl resin (ES7) having both ends and a trimeric isocyanato ring containing an epoxy group. The resin had an epoxy equivalent of 203 and was semi-solid in the absence of fluidity at room temperature.

Examples 7 to 12

Using methylated hexahydrophthalic anhydride (MH: anhydride equivalent 168 g/eq.), the equivalent ratio of epoxy resin to anhydride is 1:1. The epoxy polyoxynene resins (ES1 to 6) obtained in Examples 1 to 6 were sufficiently mixed, and then mixed with 0.5% by weight of the hardening accelerator for tetra-n-butyl fluorene, o'-diethyl Phenylphosphinodisulfate (TBDP). The mixture was degassed under vacuum, and then cured in a mold at 120 ° C for 4 hours and at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm.

Example 13

(A) component 70 parts by weight of the epoxy polyoxyl resin (ES3) obtained in Example 3 was prepared, and 3,4-epoxycyclohexenylmethyl-3', 4' for the component (D) was prepared. - epoxycyclohexene carboxylate (EpC: epoxy equivalent 130) 30 parts by weight of a resin liquid. This resin liquid was added with MH under the condition that the ratio of the epoxy equivalent to the acid anhydride equivalent was 1:1, and the TBDP for the hardening accelerator was mixed with 0.5% by weight of the entire resin mixture.

Example 14

(A) Component 70 parts by weight of EpC for the component (D) was prepared by using 70 parts by weight of the epoxy polyoxyl resin (ES4) obtained in Example 1. This resin liquid was added with MH under the condition that the ratio of the epoxy equivalent to the acid anhydride equivalent was 1:1, and the TBDP for the hardening accelerator was mixed with 0.5% by weight of the entire resin mixture.

Examples 15 to 20

Use diethyltoluenediamine (DETDA: active hydrogen equivalent 45 g/eq.), the epoxy polyoxyl resin (A) (ES1 to 6) obtained in Examples 1 to 6 was added under the condition that the ratio of the epoxy equivalent to the active hydrogen equivalent was 1:1, and the mixture was sufficiently mixed with respect to The whole was mixed with 0.5% by weight of 2-ethyl-4-methylimidazole (EIMZ) for the hardening accelerator.

Comparative example 1

In the case of using the component (A), 26 parts by weight of 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexenecarboxylate (EpC), and 34 parts by weight of MH were used. Example 7 A resin sheet was produced.

Comparative example 2

A resin plate was produced in the same manner as in Comparative Example 1, except that 20 parts by weight of triglycidyl trimeric isocyanate (EpT, epoxy equivalent 100) and 34 parts by weight of MH were used without using the component (A).

Comparative example 3

100 parts by weight of a polysulfide resin represented by ((Me ₂ CH ₂ =CH)SiO _1/2 ) _1.0 (MeSiO _3/2 ) _1.11 (Me ₂ SiO) _0.05 , and a vinyl equivalent of 1,400 g/eq 20 parts by weight of a vinyl dimethyl siloxane oil having a vinyl group and 48 parts by weight of a methylhydrogenated polyoxyxane having a hydroquinone equivalent of 64 g/eq at both ends, and a platinum for hardening catalyst is mixed with respect to the total weight - a tetraethylene dioxane complex in a xylene solution of 20 ppm.

Comparative example 4

30 parts by weight of phenyl polysulfide represented by (C ₆ H ₅ ) _0.62 (CH ₂ =CH) _0.38 (CH ₃ ) _0.38 SiO _1.31 , and the hydroquinone equivalent is 163. The g/eq methylhydrogenated polyoxyxane oil was 16 parts by weight, and 20 ppm of a platinum-tetravinyldioxane complex solution xylene solution for the hardening catalyst was mixed with respect to the total weight.

Comparative Example 5

Without using the component (A), the following general formula (15) (R ₆ SiO _3/2 ) _w (R ₇ R ₈ SiO) _x (Me ₃ SiO _1/2 ) _y (15) is used, w=0 , x=0.8, y=0.2, wherein R ₇ is a methyl group, and R ₈ is an epoxy polyoxyl resin represented by 2-(3,4-epoxycyclohexyl)ethyl (ESC, epoxy equivalent 207 A resin plate was produced in the same manner as in Example 7 except for 42 parts by weight and 27 parts by weight of MH.

Comparative Example 6

The same operation as in Example 7 was carried out, except that the component (A) was used, except that 40.6 parts by weight of the epoxy polyoxyl resin (ES6) obtained in Synthesis Example 1 and 33.6 parts by weight of MH were used, and the thickness was 1 mm and 4 mm. Resin board.

Comparative Example 7

25 parts by weight of a hydroquinone alkylation reaction product (vinyl equivalent: 250 g/eq.) of 1,3,5,7-tetramethylcyclotetraoxane with an excess of vinyl norbornene, and an excess amount 1,3,5,7-tetramethylcyclotetraoxane with vinyl hydrazine 16 parts by weight of a hydroquinone alkylation reaction product of the alkene (SiH equivalent: 160 g/eq.), and a xylene solution of a platinum-tetravinyldioxane complex according to a full weight mixed hardening catalyst 20 ppm.

The mixture obtained in Examples 7 to 20 and Comparative Examples 1 to 7 was vacuum-degassed, and then hardened in a mold at 120 ° C for 4 hours and at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. .

The physical properties of the cured resin sheet were measured by the following methods.

(1) Determination of glass transition temperature (Tg)

The thermal stress deformation measuring apparatus TMA/SS120U manufactured by Seiko Instruments Inc. was used to measure at 30 ° C to 270 ° C, and the temperature at which the linear expansion ratio was changed was used as the glass transition temperature. The heating rate was 5 ° C / min.

(2) Determination of linear expansion ratio (CTE)

The coefficient of linear expansion was calculated by measuring the inclination of a straight line obtained by joining two points of 40° C. and 60° C. using a thermal stress deformation measuring apparatus TMA/SS120U manufactured by Seiko Instruments Inc., at 30° C. to 270° C. The heating rate was 5 ° C / min.

(3) Transmittance ‧Initial transmittance (IT)

The transmittance of 400 nm of a 1 mm thick cured product was measured using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd.

‧Transparency (UVT) after UV test

Using a Q panel company weathering tester QUV, the transmittance of 400 nm of the cured product having a thickness of 4 mm after the irradiation of 600 hours of UV was measured with the initial transmittance. The UVA 340 nm of the QUV lamp was used and the black panel temperature was 55 °C.

‧ Transmittance after heat test (HRT)

The cured material having a thickness of 1 nm was exposed to an environment of 150 ° C, and the transmittance at 400 nm after 72 hours was measured with the initial transmittance.

‧ Transmittance after long-term heat resistance test (LHRT)

The cured material having a thickness of 1 mm was exposed to an environment of 150 ° C, and the transmittance at 400 nm after 480 hours was measured with the initial transmittance.

(4) Determination of hardness (Shore D)

The surface hardness of the cured product at room temperature was measured using a Tikulu (manufactured) hardness tester TYPE-D.

(5) Shape (shape) of the cured product after being taken out by the mold

After the mold was removed, the uniformity of the cured product and the cracking of the cured product due to hardening shrinkage were visually judged.

A: Uniform hardened material. B: The shape of the mold is retained but cracking occurs in the hardened material. ×: The shape of the mold was not retained, and the resin was broken.

(6) Bending and flexibility test

According to JIS-7171, a test piece of 80 mm × 10 mm × 4 mm was used, and the bending elastic modulus, bending strength, and bending flexibility were measured by an automatic clamp (manufactured by Shimadzu Corporation). Also, A indicates that it has not been broken.

The measurement results of the respective tests of the cured products obtained in Examples 7 to 20 are shown in Tables 1 and 2.

The measurement results of the respective tests of the cured products obtained in Comparative Examples 1 to 7 are shown in Table 3. Also, NM means that it cannot be measured, and RT means room temperature.

Examples 21 to 28 and Comparative Examples 8 to 14

The mixture obtained by adding the examples 7 to 14 and the comparative examples 1 to 7 was filled into a bottom-plated blue LED die-molded package by an injector, and hardened at 100 ° C for 2 hours and at 150 ° C for 5 hours. Density, making LED devices.

The physical properties of the sealed LED device were measured in the following manner.

(7) Reflow test

The sealed LED package was passed through a reflow furnace set to be held at 260 ° C for 15 seconds, and it was confirmed whether or not the sealant was colored, broken, or peeled. The results are shown in Table 4.

(8) Determination of thermal shock test

After the sealed LED package was subjected to a test at -40 ° C to 120 ° C for 500 cycles, the presence or absence of cracking and peeling of the sealant was confirmed by a microscope. The results are shown in Table 5.

In Tables 4 and 5, A means no, and X means yes. EX.7 to 14 in the additions indicate the addition of Examples 7 to 14, and CX.1 to 7 indicate the addition of Comparative Examples 1 to 7.

Diallyl isocyanuric acid is disclosed in U.S. Patent No. 2,083,051, which is obtained by dissolving triallyl isocyanurate in xylene and then using activated clay.

Monomethyl diallyl isocyanurate is disclosed in US Patent No. 2830051, in which trimethyl cyanurate is first dissolved in xylene, and after adding phenol, monomethyl cyanuric acid is synthesized using activated clay. . The resulting monomethyl cyanuric acid was synthesized in DMF solvent using allyl bromide, sodium hydroxide and tetraethylammonium for the relevant mobile catalyst.

Example 31

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and 180 parts by weight of a cyclic organosiloxane having a SiH group at both ends (SiH group is 1.36 equivalent), and dioxane 220 weight 0.83 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 37 parts by weight of diallyl cyanuric acid (with a vinyl group of 0.35 equivalent) was introduced into the reaction system over 1 hour. After confirming that the molecular weight stopped increasing by the GPC method, monoallyl diglycidyl trimerization was carried out in 1 hour. 281 parts by weight of an isocyanate (1.00 equivalent of a vinyl group) was dissolved in 280 parts by weight of a solution of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.3, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented, Z is an organic residue represented by the general formula (22), R ₂₃ is a propyl group, and R ₂₄ is a hydrogen atom. The epoxy ring of the epoxy resin (ES21) was 470 parts by weight. The resin had an epoxy equivalent of 250, a solid at room temperature, and a viscosity of 0.12 Pa‧s at 150 °C. The IR spectrum of this resin is shown in Fig. 4.

Example 32

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends is 260 parts by weight (SiH group is 1.94 equivalent), and dioxane 360 weight 1.07 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 99 parts by weight of diallyl isocyanuric acid (the vinyl group was 0.94 equivalent) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 281 parts by weight of monoallyl diglycidyl trimer isocyanate (1.00 equivalent of vinyl group) was added in one hour to dissolve the solution obtained by dissolving 281 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.9, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented, Z is an organic residue represented by the general formula (22), R ₂₃ is a propyl group, and R ₂₄ is a hydrogen atom. The base epoxy epoxide resin (ES22) was 619 parts by weight. The resin had an epoxy equivalent of 325, a solid at room temperature, and a viscosity of 0.56 Pa‧s at 150 °C. The IR spectrum of this resin is shown in Fig. 5.

Example 33

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends is 203 parts by weight (SiH group is 1.52 equivalent), and dioxane 310 weight 0.75 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 106 parts by weight of diallyl isocyanuric acid (1.01 equivalent of vinyl group) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped by the GPC method, 141 parts by weight of monoallyl diglycidyl isocyanurate (containing 0.51 equivalent of vinyl group) was dissolved in 141 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that after the absence of hydrogen gas, the remaining platinum was filtered using diatomaceous earth. catalyst. The solvent of the filtrate was distilled off using an evaporator to obtain a general formula (1). l=1, m=1, n has an average value of 2.0, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented, Z is an organic residue represented by the general formula (22), R ₂₃ is a propyl group, and R ₂₄ is a hydrogen atom. The base epoxy epoxide resin (ES23) was 398 parts by weight. The resin had an epoxy equivalent of 455, a solid at room temperature, and a viscosity of 1.61 Pa‧s at 150 °C.

Example 34

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a cyclic organic oxane having a SiH group at both ends thereof is 175 parts by weight (SiH group is 1.31 equivalent), and dioxane 210 weight 0.82 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 34 parts by weight of monomethyl diallyl isocyanate (0.31 equivalent of vinyl group) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 281 parts by weight of monoallyl diglycidyl trimer isocyanate (1.0 equivalent of vinyl group) was added in one hour to dissolve the solution obtained by dissolving 281 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into 0.1 equivalent of potassium hydroxide/methanol solution, and it was confirmed that no hydrogen was generated, and the residue was filtered using diatomaceous earth. Platinum catalyst. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.3, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented by Z, which is an organic residue represented by the general formula (22), wherein R ₂₃ is a propyl group, and R ₂₄ is a methyl group, and the terminal has an epoxy group-containing isocyanuric acid. The base epoxy epoxide resin (ES24) was 438 parts by weight. The resin had an epoxy equivalent of 250, a solid at room temperature, and a viscosity at 150 ° C of 0.08 Pa ‧ s. The IR spectrum of this resin is shown in Fig. 6.

Example 35

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a cyclic organic alkane having a SiH group at both ends is 257 parts by weight (SiH group is 1.91 equivalent), and dioxane 360 weight 107 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 102 parts by weight of monomethyl diallyl isocyanate (0.91 equivalent of vinyl group) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 281 parts by weight of monoallyl diglycidyl trimer isocyanate (1.0 equivalent of vinyl group) was charged in 1 hour, and the solution was dissolved in 281 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution. After confirming that no hydrogen was generated, the remaining platinum was filtered using diatomaceous earth. Media. The solvent of the filtrate is distilled off using an evaporator to obtain a general formula (1), l=1, m=1, n has an average value of 0.9, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented by Z, which is an organic residue represented by the general formula (22), wherein R ₂₃ is a propyl group, and R ₂₄ is a methyl group, and the terminal has an epoxy group-containing isocyanuric acid. The base epoxy epoxide resin (ES25) was 565 parts by weight. The resin had an epoxy equivalent of 327, a solid at room temperature, and a viscosity at 150 ° C of 0.11 Pa‧s. The IR spectrum of this resin is shown in Fig. 7.

Example 36

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends is 224 parts by weight (SiH group is 1.67 equivalent), and dioxane 360 weight 0.75 parts by weight of carbon-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 130 parts by weight of monomethyl diallyl isocyanate (1.17 equivalent of vinyl group) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 141 parts by weight of monoallyl diglycidyl trimeric isocyanate (containing 0.50 equivalent of vinyl group) was dissolved in 141 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into 0.1 equivalent of potassium hydroxide/methanol solution, and it was confirmed that no hydrogen was generated, and the residue was filtered using diatomaceous earth. Platinum catalyst. The solvent of the filtrate was distilled off using an evaporator to obtain a general formula (1). l=1, m=1, n has an average value of 2.0, R ₁ is a methyl group, R ₂ is a stretching propyl group, and E ₁ is a general formula. (2) The organic residue represented by Z, which is an organic residue represented by the general formula (22), wherein R ₂₃ is a propyl group, and R ₂₄ is a methyl group, and the terminal has an epoxy group-containing isocyanuric acid. The base epoxy epoxide resin (ES26) was 397 parts by weight. The resin had an epoxy equivalent of 460, a solid at room temperature, and a viscosity of 0.19 Pa‧s at 150 °C.

Example 37

In the general formula (5), R ₁ is a methyl group, l=1, m=1, and a ring-shaped organic alkane having a SiH group at both ends is 254 parts by weight (SiH group is 1.89 equivalent), and dioxane 410 weight 0.92 parts by weight of platinum-supported platinum (platinum loading 3%) was placed in a 2 L separable flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C with stirring. Next, 156 parts by weight of monomethyl diallyl isocyanurate (1,39 equivalents of vinyl group) was placed in the reaction system over 1 hour. After confirming that the molecular weight was stopped increasing by the GPC method, 141 parts by weight of monoallyl diglycidyl trimeric isocyanate (containing 0.50 equivalent of vinyl group) was dissolved in 141 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of monoallyl diglycidyl trimeric isocyanate disappeared, the reaction was dropped into 0.1 equivalent of potassium hydroxide/methanol solution, and it was confirmed that hydrogen generation could not occur, and the residue was filtered using diatomaceous earth. Platinum catalyst. The solvent of the filtrate was distilled off using an evaporator to obtain a general formula (1). l=1, m=1, n has an average value of 2.8, R ₁ is a methyl group, R ₂ is a propyl group, and E ₁ is a general formula. (2) The organic residue represented by Z, which is an organic residue represented by the general formula (22), wherein R ₂₃ is a propyl group, and R ₂₄ is a methyl group, and the terminal has an epoxy group-containing isocyanuric acid. The base epoxy epoxide resin (ES27) was 486 parts by weight. The resin had an epoxy equivalent of 575, a solid at room temperature, and a viscosity of 0.26 Pa‧s at 150 °C.

Synthesis Example 11

73 parts by weight of an organic hydrogen hydride oxysilane represented by the following formula (0.2 equivalent of SiH group), 128 parts by weight of dioxane, and 0.21 part by weight of platinum (carbon loading 3%) were placed in a stirring motor and reflux-cooled. The 500 mL separable flask of the tube and nitrogen line was heated to 100 ° C with stirring. Next, 56.2 parts by weight of monoallyl diglycidyl trimer isocyanate (0.2 equivalent of vinyl group) was added in one hour to dissolve a solution of 56 parts by weight of dioxane. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction solution was dropped into a 0.1 N KOH/methanol solution, and it was confirmed that no hydrogen gas was generated, and the remaining platinum catalyst was filtered using diatomaceous earth. The solvent of the filtrate was distilled off using an evaporator to obtain 74 parts by weight of an epoxy polyoxyl resin (ES28) having a main chain consisting of only dimethyloxane and having an epoxy group-containing trimeric isocyanato ring at both ends. The resin had an epoxy equivalent of 320, was liquid at room temperature, and had a viscosity of 5.9 Pa‧s at 25 °C.

Synthesis Example 12

72 parts by weight of 1,3,5,7-tetramethylcyclotetraoxane, 100 parts by weight of dioxane, and 0.35 parts by weight of carbon-supported platinum (3% of platinum loading) were placed in a stirring motor, a reflux cooling tube, and The 1 L separable flask of the nitrogen line was heated to 100 ° C with stirring. Next, 25 parts by weight of triallyl isocyanurate was added dropwise to the solution obtained by dissolving 25 parts by weight of dioxane in one hour. After confirming that the molecular weight was stopped by the GPC method, 112 parts by weight of 4-vinylcyclohexane oxide was added dropwise over 2 hours. After the completion of the liquid discharge, the internal temperature was raised to 110 ° C, and the reaction was carried out under reflux of dioxane. The reaction was followed by GPC. When the peak of 4-vinylcyclohexene oxide disappeared, the reaction was dropped into a 0.1 N KOH/methanol solution. After confirming that no hydrogen was generated, the residual platinum catalyst was filtered using diatomaceous earth. . 0.1 part by weight of triphenylphosphine was added to the solution, and the solvent of the filtrate was distilled off using an evaporator to obtain a trimeric isocyanato ring and a cyclic organoxanoxane skeleton in the chain of the resin, and an epoxy group at the terminal. Epoxy polyoxyl resin (ES29). The resin had an epoxy equivalent of 241.

Examples 38 to 44

The epoxy polyoxynoxy resins (ES21 to ES27) obtained in Examples 31 to 37 were added to MH under the condition that the equivalent ratio of the two was 1:1. After mixing, the TBDP used for mixing the 0.5% by weight of the hardening accelerator with respect to the whole was mixed. The mixture was degassed under vacuum, and then cured in a mold at 120 ° C for 4 hours and at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm.

Example 45

(A) Component 70 parts by weight of EpC of the component (D) was added to 70 parts by weight of the epoxy polyoxynoxy resin (ES25) obtained in Example 35 to prepare a resin liquid. The resin liquid and MH were added under the condition that the ratio of the epoxy equivalent to the acid anhydride equivalent was 1:1, and the TBDP for the hardening accelerator was mixed with 0.5 kg by weight.

Comparative Example 15

A resin plate was produced in the same manner as in Example 38 except that 32 parts by weight of the epoxy polyoxyl resin (ES28) obtained in Synthesis Example 11 and 17 parts by weight of MH were used instead of EpC.

Comparative Example 16

A resin plate was produced in the same manner as in Comparative Example 15 except that 24 parts by weight of the epoxy polyoxynene resin (ES29) obtained in Synthesis Example 12 and 17 parts by weight of MH were used instead of EpC.

The mixture obtained in Examples 38 to 45 and Comparative Examples 15 to 16 was vacuum-degassed, and then hardened in a mold at 120 ° C for 4 hours and at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. .

The physical properties of the resin sheet after hardening were measured in the same manner as above.

The tackiness is evaluated by placing the cured product in a polyethylene bag and determining that the fitter is tacky. In Tables 6 and 7, A indicates no tackiness, and × indicates tackiness.

The measurement results of the respective tests of the cured products obtained in Examples 38 to 45 are shown in Table 6.

The measurement results of the respective tests of the cured products obtained in Comparative Examples 15 to 16 are shown in Table 7.

Examples 46 to 53 and Comparative Example 18

Adding molten cerium oxide and titanium oxide for white pigment (E) to addition examples 38 to 45, and (M): molten cerium oxide: titanium oxide = 15:74:11 (wt%), and In the mixture (M) obtained in Comparative Example 2, the kneaded material was obtained by melt-kneading at 50 ° C for 10 minutes using a 2-seat roll. Next, the obtained kneaded material was cooled, and after pulverization, a thermosetting resin composition for light reflection in the form of a white solid was obtained. The composition was conveyed and formed by using a brass spacer made of 2 mm thick at a molding die temperature of 175 ° C, a molding pressure of 5 MPa, and a curing time of 300 seconds. After the mold was released from the mold, it was hardened at 150 ° C for 12 hours to make a thickness. 2 mm test piece.

Comparative Example 17, 19 to 22

Adding molten cerium oxide and titanium oxide for white pigment (E) by adding (M): molten cerium oxide: titanium oxide = 15:74:11 (wt%), adding Comparative Examples 1, 3 to 4 The mixture (M) obtained in 15 to 16 was mixed for 5 minutes at a number of revolutions of 2000 rpm using a spinning/revolving mixer to obtain a thermosetting resin composition for light reflection of a white paste. The paste composition was formed by using a true copper bran having a thickness of 2 mm and molding at a mold temperature of 175 ° C, a molding pressure of 1 MPa, and a curing time of 300 seconds. After the mold was released from the mold, it was hardened at 150 ° C. A test piece having a thickness of 2 mm was produced in 12 hours.

(11) Whether there is deformation (deformation) during demolding

When the mold was released after the conveyance molding or the press molding, it was visually confirmed whether the stress at the time of demolding caused deformation of the test piece to determine the shape retention property at the time of molding. In Tables 8 and 9, A indicates no deformation, and × indicates deformation.

(12) Determination of reflectivity ‧Infrared reflectivity (IRF)

The light reflectance at a wavelength of 460 nm was measured using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd.

‧ Reflectance (HRF) after initial heat test

The cured material having a thickness of 2 mm was exposed to an environment of 150 ° C, and the reflectance at 460 nm was measured with the initial reflectance after 72 hours.

‧ Reflectance after long-term heat resistance test (LHRF)

The cured material having a thickness of 2 mm was exposed to an environment of 150 ° C, and the reflectance at 460 nm was measured with the initial reflectance after 480 hours.

The measurement results of the white cured products obtained in Examples 46 to 53 are shown in Table 8.

The measurement results of the respective tests of the cured products obtained in Comparative Examples 17 to 22 are shown in Table 9. The mixture (M) used in Comparative Examples 17 to 22 was sequentially a mixture (M) of Comparative Examples 1 to 4 and 15 to 16.

Examples 54 to 61 and Comparative Examples 23 to 28

The mixture obtained by adding the examples 38 to 45 and the comparative examples 17 to 22 was filled in a blue LED package with a bottom silver plated electrojunction light-emitting device by means of an injector, and was dried at 100 ° C for 2 hours and at 150 ° C for 5 hours. The conditions were hardened and sealed to produce an LED device.

The sealed LED device was subjected to a reflow test, and the results were shown in Table 10, and a thermal shock test was performed. The results are shown in Table 11. The test conditions and the meanings of the symbols in the table are the same as in Tables 4 and 5.

Industrial use possibility

The epoxy polyoxynene resin of the present invention has excellent surface hardness, strength, and flexibility and is excellent in heat resistance when it is used as a curable resin composition, and has excellent heat resistance. , a light-resistant colored hardened or film. Therefore, it is suitable for electronic component materials such as semiconductors and circuit boards, and optical member materials such as optical lenses, optical sheets, and white reflective materials for light reflection, and in particular, it is expected to improve the color or heat of the current LED sealing materials. Cracking, wire breakage, and peeling from the substrate during reflow or thermal cycling.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an IR spectrum of an epoxy polyoxynene resin (ES1) of the present invention.

Figure 2 is an IR spectrum of the epoxy polyoxynene resin (ES3) of the present invention.

Figure 3 is an IR spectrum of the epoxy polyoxynene resin (ES5) of the present invention.

Figure 4 is an IR spectrum of the epoxy polyoxynene resin (ES21) of the present invention.

Figure 5 is an IR spectrum of the epoxy polyoxynene resin (ES22) of the present invention.

Figure 6 is an IR spectrum of the epoxy polyoxynene resin (ES24) of the present invention.

Figure 7 is an IR spectrum of the epoxy polyoxynene resin (ES25) of the present invention.

Claims (15)

An epoxy polyoxynene resin characterized by the general formula (1) having an epoxy equivalent of 200 to 2000 g/eq. (wherein R ₁ represents a hydrocarbon group having a carbon number of 1 to 10, which may be the same or different; and R ₂ represents a hydrocarbon group having a carbon number of 1 to 20 and may have 1 to 3 ether linkages inside. An oxygen atom; E ₁ is a monovalent organic residue represented by formula (2); Z represents a divalent organic residue; l, m is independently an integer of 0 to 3, and conforms to 1≦l+m≦4; n is 0<n≦100), The epoxy polyoxyxene resin according to claim 1, wherein Z in the general formula (1) is a divalent organic residue represented by the general formula (3) or the general formula (4), Wherein R ₃ represents a methyl group or a phenyl group, which may be the same or different; k is a number from 0 to 100; R ₄ represents a methyl group or a phenyl group, which may be the same or different; i, j are independently 0. To an integer of 3, and 1≦i+j≦4). An epoxy polyoxyxene resin according to claim 1, wherein Z in the general formula (1) is a divalent organic residue having a trimeric isocyanato ring represented by the general formula (22), (wherein R ₂₃ represents a hydrocarbon group having 1 to 10 carbon atoms; and R ₂₄ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). The invention relates to a method for producing an epoxy polyoxyxene resin, which is a method for producing an epoxy polyoxyxene resin according to claim 1, which is characterized in that a compound having a vinyl group at both ends of the theoretical amount is not used. a cyclic organooxane reaction containing SiH groups at both ends represented by the formula (5), and then a monoallyl diglycidyl trimer isocyanate is used to carry out a terminal sealing reaction on the remaining SiH groups. (wherein, R ₁ , l, m are synonymous with the general formula (1)). The method for producing an epoxy polyoxyxene resin according to claim 4, wherein the compound having a vinyl group at both ends is a polyorganic compound having a vinyl group at both ends represented by the general formula (6) or the general formula (7). Oxane, Wherein R ₃ represents a methyl group or a phenyl group, which may be the same or different; k is a number from 0 to 100; R ₄ represents a methyl group or a phenyl group, which may be the same or different; i, j are independently 0. To an integer of 3, and 1≦i+j≦4). The method for producing an epoxy polyoxyxene resin according to claim 4, wherein the compound having a vinyl group at both ends is a trimeric isocyanic acid derivative having a vinyl group at both ends represented by the general formula (25). (wherein R ₂₅ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R ₂₆ represents a hydrocarbon group having 1 to 8 carbon atoms; and R ₂₇ represents a hydrogen atom or a methyl group). A thermosetting resin composition characterized by epoxy resin The hardener (B) and the hardening accelerator (C) are essential components of the thermosetting resin composition, and the epoxy resin component contains the epoxy polyoxyl resin of the epoxy polyoxyl resin as claimed in claim 1. Resin (A). The thermosetting resin composition of claim 7, wherein the hardener (B) is an acid anhydride or a liquid amine compound at room temperature. The thermosetting resin composition of claim 7, wherein the hardening accelerator (C) is a grade 4 ammonium salt or a grade 4 phosphonium salt. The thermosetting resin composition of claim 7, wherein the epoxy resin component comprises an epoxy polyoxyalkylene resin (A) and a liquid epoxy resin (D) at room temperature, and is opposite to the ring. 100 parts by weight of the oxygen polyoxygen resin (A), 5 to 150 parts by weight of the epoxy resin (D) at room temperature, and an epoxy equivalent of the epoxy resin mixture of 180 to 1000 g/eq. A thermosetting resin composition which is a thermosetting resin composition according to claim 7 of the patent application, further contains a white pigment (E). The thermosetting resin composition of claim 11, wherein the white pigment is at least one selected from the group consisting of cerium oxide, titanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and inorganic hollow particles. The thermosetting resin composition of the seventh aspect of the invention, wherein the thermosetting resin composition is a resin composition for an optical member, a resin composition for an electronic member, or a resin composition for an optical semiconductor member. The thermosetting resin composition according to claim 7, wherein the thermosetting resin composition is a liquid sealing resin composition for a semiconductor. An LED device characterized by using a thermosetting resin composition as claimed in claim 13 of the patent application.