WO2015133840A2 - Composé époxy ayant un groupe alcoxysilyle, son procédé de préparation, composition le contenant, produit durci, et son utilisation - Google Patents

Composé époxy ayant un groupe alcoxysilyle, son procédé de préparation, composition le contenant, produit durci, et son utilisation Download PDF

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WO2015133840A2
WO2015133840A2 PCT/KR2015/002138 KR2015002138W WO2015133840A2 WO 2015133840 A2 WO2015133840 A2 WO 2015133840A2 KR 2015002138 W KR2015002138 W KR 2015002138W WO 2015133840 A2 WO2015133840 A2 WO 2015133840A2
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formula
integer
group
epoxy
epoxy compound
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PCT/KR2015/002138
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English (en)
Korean (ko)
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WO2015133840A3 (fr
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전현애
김윤주
탁상용
박수진
박숙연
박성환
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한국생산기술연구원
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Priority claimed from KR1020150028082A external-priority patent/KR101749551B1/ko
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Publication of WO2015133840A2 publication Critical patent/WO2015133840A2/fr
Publication of WO2015133840A3 publication Critical patent/WO2015133840A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to an epoxy compound having an alkoxysilyl group via a new spacer group exhibiting excellent heat resistance and improved brittleness, a process for its preparation, a composition comprising the same, a cured product and its use. More specifically, the present invention provides good heat resistance properties in composites, specifically low thermal expansion properties and high glass transition temperatures (including Tg leases that do not exhibit glass transition silver), improved brittleness and / or flame retardancy in cured products.
  • the present invention relates to a new epoxy compound having a spacer between a core and an alkoxysilyl group, which does not require a separate silane coupling agent, a preparation method thereof, a composition comprising the same, a cured product, and a use thereof. '
  • Epoxy resins have a much larger coefficient of thermal expansion, several times to several tens, than ceramic and metal materials. Therefore, when the epoxy resin is used together with the inorganic material or the metal material, the physical properties and workability of the part are significantly limited due to the different coefficients of thermal expansion of the epoxy resin and the inorganic material or the metal material. For example, during semiconductor packaging where silicon wafers and epoxy substrates are used adjacent to each other, there is a significant difference in the coefficient of thermal expansion (CTE-mi sniatch) between components, resulting in crack generation, warpage and peeling of the substrate. f) Product defects such as breakage of the substrate.
  • CTE-mi sniatch coefficient of thermal expansion
  • the size of the inorganic particles tends to decrease due to the miniaturization of the semiconductor structure, but the viscosity increase problem becomes more serious when a filler of 1 or less is used. And, when the inorganic particles having a large average particle diameter are used, the frequency of unfilling at the application site of the composition containing the resin and the inorganic particles increases.
  • the CTE of the epoxy composite is greatly reduced, but still shows a high CTE compared to silicon chips and the like.
  • the high CTE of current epoxy materials limits the production of highly integrated electronic components such as next-generation semiconductor substrates and PCBs. Therefore, low CTE to improve the heat resistance insufficient due to the high CTE of the conventional epoxy composite and There is a need for the development of epoxy composites having excellent glass transition temperature characteristics as well as improved brittleness.
  • the improved heat resistance properties in the composite specifically low CTE and high.
  • Epoxy compounds are provided having alkoxysilyl groups via spacer groups which exhibit glass transition silver, improved brittleness and / or good flame retardancy in the cured product.
  • a manufacturing method is provided.
  • an epoxy compound having an alkoxysilyl group via a spacer groupol exhibiting improved heat resistance in the composite, specifically low CTE and high glass transition temperature, improved brittleness and / or excellent flame resistance in the cured product there is provided an epoxy composition comprising a. Furthermore, according to another aspect of the present invention, a composite having an alkoxysilyl group via a spacer group exhibiting improved heat resistance properties, specifically low CTE and high glass transition temperature, improved brittleness and / or excellent flame retardancy in the cured product. A cured product of an epoxy composition comprising an epoxy compound is provided. In addition, according to another aspect of the present invention. According to one aspect of the invention. According to one aspect of the invention there is provided the use of an epoxy composition comprising an epoxy compound having an alkoxysilyl group via a spacer group. 15002138
  • an epoxy compound having an alkoxysilyl group via a spacer wherein the core further comprises at least one substituent selected from the group consisting of hydrogen, a hydroxy group and an alkenyl group.
  • the hydroxy group is independently selected from the group consisting of -OH, -0- (CH 2 ), -0H and-(C) ⁇ 0H, wherein 1 is an integer from 1 to 10.
  • an epoxy compound having an alkoxysilyl group via a spacer According to the fourth opinion,
  • an epoxy compound having an alkoxysilyl group via a spacer wherein the alkenyl group is of the general formula A5, A6, A7 or A8. .
  • Epoxy compound having an alkoxysilyl group via a spacer according to any one of claims 1 to 4, wherein the core is triphenylmethane, binaphthalene, tetraphenylethane, aromatic amine, cycloaliphatic amine or novolak unit. This is provided. According to the sixth aspect,
  • an epoxy compound having an alkoxysilyl group via a spacer wherein the core is selected from the group consisting of the following formulas AC to KC.
  • K is a direct linkage, -CH 2 -or
  • Ry is a straight or branched chain alkyl group of CI— CIO
  • R is H or CI— C3 alkyl
  • n is an integer of 2 or more
  • L is lfc
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer greater than or equal to
  • N is an integer of 1 or more
  • the cores of the formulas AC to CC are connected to the linking group LG1
  • the formulas HC to The core of KC has an alkoxysilyl group via a spacer which is linked to the following linker LG
  • Epoxy compounds are provided. ⁇
  • the epoxy compound is provided with an epoxy compound having an alkoxysilyl group via a spacer, which is one of the following formulas AF to KF.
  • At least two of the plurality of substituents A is the formula E1, at least one A is the formula A1 or A2, and if there is a residual substituent A, -OH, -0- (CH 2 ) ⁇ 0H (1 is an integer from 1 to 10), each independently selected from the group consisting of Formulas A5 and A6, wherein in Formulas HF to KF, at least two substituents A are at least one of Formula E2: At least one A is of formula A3 or A4, and if there is a residual substituent A, it is -H,-(CHs -OH l is an integer of 1 to 10), each independently from the group consisting of formulas A7 and A8 In formula CF, K is a direct linkage, ⁇ CH 2 -or
  • Ry is a straight-chain or branched alkyl group of Cl-ClO, wherein in formula HF, Q is -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2 —, -S-, ⁇ S0 2 -again " And each R is independently H or C1-C3 alkyl.
  • n is an integer of 2 or more.
  • N is an integer of 1 or more when L is 1F
  • n is an integer of 1 or more
  • n 0 or an integer of 1 or more
  • M is
  • n is an integer greater than or equal to 2 :
  • n is an integer greater than or equal to 1
  • p is 1 or 2.
  • alkyl and alkoxy groups may be straight linear or branched, cyclic Or may be acyclic, with or without at least one heteroatom selected from the group consisting of N, 0, S, and P,
  • I is an integer from 1 to 10
  • n 1 to 8.
  • the epoxy compound of the formula (AF) to CF is connected to a linking group of the formula
  • the epoxy compound of the formula HF to KF is provided with an epoxy compound having an alkoxysilyl group via a spacer, which is connected to the linking group of formula LG2.
  • a second step of forming the intermediate product I and to 'any one of the epoxy compound of the formula AF to KF to by reacting an alkoxysilane of the formula R2 A method for producing an epoxy compound having an alkoxysilyl group via a spacer is provided.
  • J is hydrogen, a hydroxyl group, a straight or branched chain alkyl group of C1 to C10 or an aromatic group of C6 to C10,
  • CS K is a single bond (di rect l inkage), -C3 ⁇ 4- or
  • Ry is a straight-chain or branched alkyl group of ci-cio, wherein in the above formula HS, Q is CH 2 ⁇ ⁇ -C (CH 3 ) 2 — , — C (CF 3 ) 2 —, — S—, _S0 2- , or
  • R is independently H or C1-C3 alkyl
  • n is an integer of 2 or more.
  • N is an integer greater than or equal to 1 when L is lfs
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer greater than or equal to 2
  • n is an integer of 1 or more
  • X is CI, Br, I, -0-S0 2 -CH 3 , -0-S0 2 -CF 3. Or -0-
  • At least two of the plurality of substituents D are the following formula E1, at least one D is -C CH 2 ) ⁇ 0H (wherein 1 is an integer of 1 to 10), and the remaining substituents If D is present, it may be -0H, and in Formulas HM1 to KM1, at least two of the plurality of substituents D are of Formula E2, and at least one D is-(CH 2 ) ⁇ 0H (wherein 1 is 1) To an integer of 10 to 10), and if there is a residual substituent D, it may be hydrogen, and in Formula AMI, J is hydrogen, a hydroxyl group, a straight or branched chain alkyl group of C1 to, or an aromatic group of C6 to C10, K is a single bond (direct inkage l) in,, -CH 2 - or (Rx is H black is a C1-C3 alkyl group),
  • L is.
  • Ry is a C1-C10 straight or branched alkyl group
  • Q is -CH 2- , —C (CH 3 ) 2 _, -C (CF 3 ) 2- , -S-, -S0 2 _. or
  • Each R is independently H or C1-C3 alkyl
  • n is an integer of 1 or more
  • n is an integer of 1 or more.
  • n is 0 or an integer of 1 or more.
  • n is an integer of 2 or more
  • p is 1 or 2.
  • At least one of to 3 ⁇ 4 is a C1-C6 linear, branched or cyclic alkoxy group, the remaining substituents are C1-C10 linear, branched or cyclic alkyl group, N, 0, S, And at least one hetero atom selected from the group consisting of P, m is an integer from 1 to 8)
  • At least two of the multivalent substituents A are the following formula E1, at least one A is the formula A2, and if there is a residual substituent A, -0H,-()-((3 ⁇ 4)! — 0H (wherein 1 is an integer from 1 to 10),
  • At least two of the plurality of substituents A are the following Formula E2, and at least one A is the following Formula A4, and if there is a residual substituent A, it is (CH 2 ) ⁇ 0H (wherein 1 is 1 to 1). Is an integer of 10), and in the above formula AF, J is hydrogen, a hydroxy group, a straight or branched chain alkyl group of C1 to C10 or an aromatic group of C6 to C10, and in the formula CF, K is a di rect l inkage,- CH 2 -or
  • Ry is a straight-chain or branched alkyl group of ci-cio :
  • Q is-(: 3 ⁇ 4-, -C (CH 3 ) 2- , -C (CF 3 ) 2 ⁇ , -S-,- S0 2 ⁇ or
  • each R is independently H or C1-C3 alkyl
  • n is an integer of 2 or more
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer of 2 or more
  • n is an integer greater than or equal to 1
  • p is 1 or 2.
  • At least one of to 3 ⁇ 4 is a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, the rest is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, N, May or may not have at least one hetero atom selected from the group consisting of 0, S, and P,
  • 1 is an integer from 1 to 10
  • n is an integer of 1 to 8)
  • J in the formula AS is hydrogen. Hydroxy group, C1 to C10 straight or branched chain alkyl group or C6 to C10 aromatic group,
  • K is a single bond (di rect l inkage), -CH 2 — or
  • Each R is independently H or C1-C3 alkyl
  • n is an integer of 2 or more. If L is lfs. n is an integer of 1 or more.
  • n is an integer of 1 or more
  • n is 0 ' or an integer of 1 or more
  • n is an integer of 2 or more
  • n is an integer of 1 or more
  • X is CI, Br, I, — ⁇ — S0 2 -CH 3 , -0_S0 2 -CF 3 , or -0-
  • At least two of the plurality of substituents D is the formula E1, at least one D is -CU rOH (wherein 1 is an integer of 1 to 10), if there is a residual substituent D, It may be — 0H, wherein in Formulas HM1 to KM1, at least two of the plurality of substituents D are of formula E2, wherein at least one D is — (CH 2 ) ⁇ 0H (wherein 1 is an integer from 1 to 10).
  • ⁇ 0 is in the formula CM1 K is a single bond (di rect l inkage) -CH 2 -or (RH or CI ⁇ C3 alkyl)
  • Ry is a C1-C10 straight or branched alkyl group.
  • Q is — (3 ⁇ 4-, ⁇ C (C3 ⁇ 4) 2- , ⁇ C (CF 3 ) 2- , -S-, -S0 2 —, again
  • Each R is independently H black is C1-C3 alkyl
  • n is an integer of 2 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more.
  • n is an integer greater than or equal to
  • N is an integer of 1 or more
  • p is 1 or 2.
  • Y is CI, Br I, -O-SO2-CH3, -O-SO2-CF3, or-is S02-C 6 H 4 -C3 ⁇ 4, and is an integer of 8
  • At least two of the plurality of substituents E are the following Formula E1, and at least one E is-(HCH ⁇ -CHCH r KH ⁇ where 1 is an integer of 1 to 10, m is 1 -OH,-(HCH 2 ),-0H (wherein 1 is an integer of 1 to 10), and -0- (CH 2 ) m -CH
  • at least two of the plurality of substituents E are of Formula E2 E is (CH 2 ) ⁇ 0— (C3 ⁇ 4)
  • Ry is a C1-C10 straight or branched alkyl group
  • Q is -CH 2- , -C (CH 3 ) 2- , — C (CF 3 ) 2 — , -S_, _S0 2 — , and :
  • R is independently H or CI— C3 alkyl
  • n is an integer of 2 or more
  • n is an integer of 1 or more.
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer greater than or equal to 2
  • p is 1 or 2.
  • At least one of to 3 ⁇ 4 is a linear, branched or cyclic alkoxy group of C1-C6 and the rest are independently a linear, branched or cyclic alkyl group of C1-C10, N, 0, S, And may have or may not have at least one hetero atom selected from the group consisting of P)
  • At least two of the plurality of substituents A is the formula E1
  • at least one A is the formula A1
  • if there is a residual substituent A, -0H, — CKCH ⁇ !-OH (wherein 1 is an integer of 1 to 10), each independently selected from the group consisting of Formulas A5 and A6, wherein in Formulas HF to KF, at least two of the plurality of substituents A are Formula E2, and at least one A is a chemical formula A3, and, if there is a residual substituent A, -H,-(C3 ⁇ 4) i-0H, where 1 is an integer from 1 to 10.
  • J is a hydrogen ⁇ hydroxy group, a straight or branched chain alkyl group of C1 to C10 or an aromatic group of C6 to C10, wherein in Formula CF, K is a direct linkage, -CH 2 -or (Rx is H or C1-C3 alkyl group),
  • Q is -CH 2 ⁇ , -C (.C3 ⁇ 4) 2- , ⁇ C (CF 3 ) 2 ⁇ , -S_, -S0 2- , or R is independently H or C1-C3 alkyl,
  • n is an integer of 2 or more
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer greater than or equal to 2
  • n is an integer of 1 or more
  • p is 1 or 2.
  • At least one of is a linear. Branched or cyclic alkoxy group having 1 to 6 carbon atoms, the rest is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, N, 0 May have or may not have at least one heteroatom selected from the group consisting of S, and P,
  • the first step is a "two bars the alkyl hydroxy compound is first banung. Thereafter, a method for producing an epoxy compound having an alkoxysilyl group via a spacer is provided, wherein the epichlorohydrin is added and reacted continuously in situ. According to point thirteen,
  • the first step is performed through a spacer in which the starting material and the epichlorohydrin are reacted first, and then the alkylhydroxy compound is continuously added and reacted in situ.
  • a method for producing an epoxy compound having an alkoxysilyl group is provided. According to my 14th opinion.
  • the first step includes the step of reacting and reacting the starting material and the alkylhydroxy compound (1-la); .
  • step (1-la) of the product as banung epi chlorohydrate is a method for producing an epoxy compound with step (l_2a) is performed in which, by an alkoxysilyl group via a spacer which is provided by the i banung.
  • the first step comprises the steps of reacting the starting material and the epichlorohydrin (1-lb); And the semi-product of step (1-lb) with the alkylhydroxy compound.
  • a method for producing an epoxy compound having an alkoxysilyl group via a spacer which is carried out by reacting (1 ⁇ 2b). According to the sixteenth opinion.
  • an epoxy composition comprising an epoxy compound having an alkoxysilyl group via the spacer of any one of claims 1 to 9. According to view 17,
  • the epoxy composition containing the epoxy compound of Claim 16 whose ratio of the total epoxy group: alkoxysilyl group of the epoxy compound contained in the said epoxy composition is 1: 5-20: 1 is provided. According to view 18,
  • An epoxy composition further comprising at least one epoxy compound selected from the group consisting of glycidyl ether epoxy compounds, glycidyl based epoxy compounds, glycidyl amine epoxy compounds, and glycidyl ester epoxy compounds.
  • the epoxy compound is bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, 1, 1, 2, 2-tetra as a core structure
  • Epoxy compositions having phenylethane, tetraphenylmethane, 4, 4'-diaminodiphenylmethane, aminophenols, cycloaliphatic, aliphatic, or novolac units are provided. According to my 20th opinion,
  • the epoxy compound, glycidyl ether type epoxy compound, glycidyl type epoxy compound, glycidylamine type epoxy compound having an alkoxysilyl group via the spacer based on the total weight of the epoxy compound compound, and the glycidyl-epoxy composition contains at least a kind of an epoxy compound Owt% to 99wt% selected from the group consisting of pyridyl ester-based epoxy compound, i. According to view 21,
  • an inorganic particle as a filler Or an epoxy composition further comprising a fiber.
  • the inorganic particle is at least one epoxy selected from the group consisting of at least one metal oxide selected from the group consisting of silica, zirconia, titania, alumina, silicon nitride and aluminum nitride, and silsesquioxane.
  • a composition is provided. According to opinion 23,
  • an epoxy composition further comprising inorganic particles is provided.
  • An electronic material comprising the epoxy composition according to any one of items 16 to 24. According to view 26,
  • a semiconductor device including the printed wiring board of the 29th aspect is provided. According to opinion 31,
  • An adhesive comprising the epoxy composition of any of claims 16-24.
  • a paint comprising the epoxy composition of any one of claims 16-24. According to 35th opinion,
  • positioned at the 36th prepreg is provided. According to 38,
  • a cured product o of an epoxy composition of any of claims 16 to 24 is provided. According to 39th opinion,
  • cured material of Claim 38 WHEREIN The said hardened
  • the cured product is a cured product of the epoxy composition does not exhibit a glass transition temperature of the higher or a glass transition temperature greater than 100 o C, is provided.
  • Epoxy compositions comprising epoxy compounds are characterized in that, in composites and / or cured products, the improved heat resistance properties, ie, the CTE of the epoxy composites are reduced and do not exhibit a glass transition temperature rise or glass transition temperature (hereinafter referred to as 'Tg lease'). Effect. Furthermore, it exhibits improved brittleness due to the flexible spacer between the core and the alkoxysilyl group. Moreover, the alkoxysilyl group via the spacer group which concerns on this invention .
  • the present invention provides improved heat resistance at the time of formation of the composite by curing the epoxy composition, specifically low CTE and high T g (including Tg lease), improved brittleness and / or good flame retardancy in the cured product and a separate silane coupling agent.
  • composite refers to a cured product of a composition comprising an epoxy compound, a curing agent, and a filler (fibers and / or inorganic particles).
  • the term “cured product” refers to a cured product of a composition comprising an epoxy compound and a curing agent, and is composed of a filler, an optional additional curing agent, an optional curing catalyst, and other additives in addition to the epoxy compound and the curing agent.
  • a cured product of the composition comprising at least one selected from the group.
  • Semi-rigids may include: In general, since the cured product reinforced with inorganic particles and / or fibers is called a composite, the cured product has a broader meaning than the composite, but the cured product reinforced with inorganic particles and / or fibers may have It may be understood in the same sense.
  • the epoxy compound having an alkoxysilyl group via the spacer group according to the present invention exhibits low CTE and high glass transition temperature or Tg-less (less), thereby improving dimensional stability. Furthermore, the flexible spacer exhibits improved brittleness. Moreover, the hardened
  • Epoxy compounds having alkoxysilyl groups via new spacer groups in accordance with one aspect of the present invention include alkoxysilyl via at least two epoxy groups and at least one spacer group in the core. Groups (hereinafter also referred to only as 'alkoxysilyl groups'), ie at least one alkoxysilyl group connected to the core via a spacer.
  • the epoxy compound having an alkoxysilyl group via the spacer group may optionally additionally have in the core an algal subphase selected from the group consisting of hydrogen, hydroxy groups and alkenyl groups, ie at least one group:
  • the epoxy group may be to the general formula E1 or E2, epoxy ⁇ 'compounds of the invention may comprise at least two said ⁇ or E2,
  • the alkoxysilyl group via the spacer group may be selected from the group consisting of the following formulas Al, A2, A3 and A4.
  • At least one of 3 ⁇ 4 is carbon number.
  • An alkyl group of 10 is preferably an alkyl group with 1 to 5 carbon atoms, wherein the alkyl group and the alkoxy group may be linear or branched, may be cyclic or acyclic, and are selected from the group consisting of N, 0, S, and P. It may or may not have at least one hetero atom selected.
  • 1 is an integer of 1-10, m is 1-8, Preferably it is an integer of 1-4. .
  • the additional hydroxyl group may be independently selected from the group consisting of —OH, —0- (CH 2 ) 0H and ⁇ ((:) “0H, and any additional alkenyl group may be represented by Formula A5, A6, A7 or A8 Wherein 1 is an integer from 1 to 10.
  • the core is understood to include not only structures represented by the following formulas AC to CC and HC to KC, but also represented by repeating units such as DC to GC.
  • (KC) J in the formula AC is hydrogen, hydroxy group, C1 to C10 linear or branched alkyl group, or C6 to C10 aromatic group,
  • K is a direct linkage, ⁇ CH 2 -or
  • Q in the formula HC is -CH 2- , -C (C3 ⁇ 4) 2 2 , -C (CF 3 ) 2 —, -S-, -S0 2- , or Go.
  • R is H or C1-C3 alkyl, in the formula DC, when L is lac to lfec.
  • n is an integer of 2 or more,
  • n is an integer of 1 or more.
  • N is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n is an integer greater than or equal to 2 c H
  • n is an integer of 1 or more
  • an upper limit of n value is 1000.
  • the core selected from the group consisting of AC to: CC and HC to KC may have a dimer or more structure, and how about two or more cores are connected to the linking group (LG). Can be connected. If necessary, 1 to 1,000 core structures may be further connected.
  • two or more identical cores selected from Formulas AC to CC may be connected to a linking group of Formula LG1
  • two or more identical cores selected from Formulas HC to KC may be connected to a linking group of Formula LG2.
  • the epoxy compound having an alkoxysilyl group via the new spacer group according to the present invention may be represented by the following formulas AF to KF.
  • At least two of the plurality of substituents A are of the formula E1, at least one A is of the formula A1 or A2, and if there is a residual substituent A, it is -OH, -0- ( CH 2 ) ⁇ 0HO is an integer of 1 to 10), and each independently selected from the group consisting of Chemical Formulas A5 and A6.
  • At least two of the plurality of substituents A are the formula E2, at least one A is the formula A3 or A4, and if there is a residual substituent A, -H,-( ⁇ , - ⁇ ⁇ is an integer of 1 to 10), and each independently selected from the group consisting of Formulas A7 and A8.
  • J is hydrogen, a hydroxyl group, a straight or branched chain alkyl group of C1 to C10 or C6 to C10. Is an aromatic group of
  • K is a single bond (di rect l inkage), -CH 2 -or (Rxfe H black is a CI- C3 alkyl group), L in the formula DF
  • Ry is a straight or branched chain alkyl group of CI— CIO, wherein in formula HF, Q is —CH 2 _, -C (C3 ⁇ 4) 2- , -C (CF 3 ) 2 ⁇ , -S-, -S0 2 ⁇ , or
  • R is each independently H or C1-C3 alkyl.
  • n is an integer of 2 or more
  • L is IF
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • n 2 or more
  • n is an integer of 1 or more
  • n 1 or 2.
  • the upper limit of n value is 1000.
  • an epoxy compound may be connected by the linking group (LG).
  • the epoxy compounds of Formulas AF to CF may be a linking group of Formula LG1.
  • the epoxy compounds of Formulas HF to KF may be connected to a linking group of Formula LG2.
  • At least two of the plurality of substituents A of the epoxy compounds of Formulas AF to GF are of Formula E1, at least one is of Formula A1 or A2, and if there are residual substituents A, OH, -0- (CH ⁇ rOHU is an integer of 1 to 10), each independently selected from the group consisting of the formula A5 and A6. .
  • At least two of the plurality of substituents A of the epoxy compound of Formulas HF to KF are the above.
  • Formula E2 at least one of which is Formula A3 or A4 above, with the remaining substituent A.
  • an epoxy composition comprising a novel epoxy compound according to any aspect of the invention described above.
  • the total epoxy group: alkoxysilyl group ratio of the epoxy compound included in the epoxy composition in the composition including the new epoxy compound may be 1: 5 to 20: 1.
  • alkoxy group is a monovalent group which is -OR (R is an alkyl group), which may be linear or branched.
  • alkyl group refers to a monovalent hydrocarbon group, which may be straight or branched.
  • each substituent may be independently selected.
  • R1 to R3 of A1 may be the same or different.
  • epoxy compounds having an alkoxysilyl group via a spacer group exhibit low CTE and high glass transition temperature or Tg-less in the composite of the composition including the same.
  • the spacer group is a structure including "-(CH ⁇ rO—", and is a flexible spacer of a portion of the alkoxysilyl group bonded to the core when the alkoxysilyl group is connected to the core via such a structure.
  • the spacer group With-(CH 2 ) i-0-, improved brittleness is indicated.
  • a method for producing epoxy compound having alkoxysilyl group via spacer group of the above formulas AF to KF is provided. Specifically, the formulas AF to KF and the epoxy compound introduce at least two epoxy groups and at least one flexible spacer group into the starting material (first step), and then introduce an alkoxysilyl group into the hydroxy group at the terminal of the flexible spacer group.
  • a method by the step (second step) of doing (hereinafter, referred to as 'method 1'); And introducing at least two epoxy groups and at least one flexible spacer group into the starting material (first step) , and then alkylating the hydroxy group at the ends of the flexible spacer group.
  • each method is explained concretely.
  • Method 1 (Introduction of Alkoxysilyl Group by Isocyanate Silane Coupling Agent)
  • An epoxy compound having an alkoxysilyl group via the spacer group of the present invention first introduces at least two epoxy groups and at least one spacer group (alkylhydroxy group) into the starting material. (Step 1) and thereafter. It can be prepared by the method by the step of silylating the hydroxyl group at the terminal of the spacer group (second step).
  • at least two epoxy groups and at least one flexible spacer are introduced into the starting material by reaction of the starting material of any one of Formulas AS to KS, an alkylhydroxy compound of Formula R1, and epichlorohydrin.
  • the first step reaction of Method 1 may be carried out by (1) introducing a epoxy group and a flexible spacer group in a single step, and (2) introducing an epoxy group and a flexible spacer group in a separate step.
  • the alkylhydroxy compound of the formula R1 is used for 1 equivalent of the hydroxy group and / or the amine group of the starting material of any one of Formulas AS to KS.
  • the alkylhydroxy compound of the formula R1 and epichlorohydrin added in situ.
  • the alkyl hydroxy compound and epachlorohydrin can be added or reacted in situ simultaneously or sequentially.
  • the starting material When added sequentially, the starting material reacts with the alkylhydroxy compound first, followed by the addition of epichlorohydrin in situ; Or react the starting material and epichlorohydrin first and then.
  • Intermediate I can be obtained by reacting by adding an alkylhydroxy compound in situ. The starting material and the alkylhydroxy compound are first reacted in that the epoxy compound generation control of the dimer or more is easy. It is preferred to react by adding epichlorohydrin in situ to obtain intermediate I.
  • the first step reaction can also be carried out sequentially with the reaction with the alkylhydroxy compound and with the epichlorohydrin in separate and different steps.
  • the amount of alkyl hydroxy compound and epichlorohydrin used for the starting material is the same as the amount used in a single step at the original position. Article.
  • the epichlorohydrin may be used in excess to act as reactants and solvents.
  • J is hydrogen, a hydroxyl group, a straight or branched chain alkyl group of C1 to C10 or an aromatic group of C6 to C10,
  • CS K is a single bond (di rect l inkage), ⁇ C3 ⁇ 4- or
  • Rx is H black is a C1-C3 alkyl group
  • Ry is a C1-C10 linear or branched alkyl group
  • Q is -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- . -S-, -S0 2 — , or
  • n is an integer of 2 or more
  • L is lfs
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • the upper limit of n value is 1000.
  • the alkylhydroxy compound may be represented by the following formula R1.
  • X in formula R1 is CI, Br, I, -O-SO2-CH3, -O-SO2-CF3, or -0—
  • S0 2 ⁇ C 6 H 4 -CH 3 and 1 is an integer from 1 to 10.
  • At least two of the plurality of substituents D is El, the at least one D is-(CH 2 ) ⁇ 0H (wherein 1 is an integer of 1 to 10), and the remaining substituents If D, then it may be -0H.
  • at least two of the plurality of substituents D are of the formula E2, at least one of D is-(C3 ⁇ 4) i-0H (wherein 1 is an integer of 1 to 10), and the remaining substituents D are If present, it may be hydrogen.
  • J is hydrogen, a hydroxy group, a straight or branched chain alkyl group of C1 to C10 or an aromatic group of C6 to C10, and in Formula CM1, K is a single bond (direct l inkage), — C3 ⁇ 4 ⁇ or (Rx is H black is a C1-C3 alkyl group),
  • Ry is a C1-C10 straight or branched alkyl group
  • Q is-(3 ⁇ 4-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -S-, -S0 2 ⁇ , or
  • n is an integer of 2 or more
  • L is lDf
  • n is an integer of 1 or more
  • n is an integer of 1 or more
  • N is an integer greater than or equal to 2.
  • N is an integer of 1 or more
  • p is 1 or 2.
  • the upper limit of n value is 1000.
  • the first stage reaction can be carried out in the presence of a base and any solvent.
  • the intermediate product I of any one of Formulas AMI to KM1 is obtained by reacting at room temperature to 100 ° C. for 1 to 120 hours.
  • the degree of reaction and the reaction time of the first step receiving depends on the kind of reactant, but, for example,
  • KOH, NaOH, K 2 CO 3 , Na 2 CO 3 , KHC0 3 , NaHC0 3 , NaH, triethylamine and diisopropylethyl amine can be mentioned.
  • These bases may be used alone or in combination of two or more of them.
  • the base is preferably used in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxy group and / or amine group of the starting material in terms of reaction efficiency.
  • the solvent may be optionally used if necessary.
  • the solvent may not be used if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without the need for a separate solvent in the first step reaction.
  • a separate solvent is not required, which can be easily determined by those skilled in the art.
  • a solvent as a possible solvent, a semicoal water can be dissolved well, and any organic solvent can be used as long as it can be easily removed after the reaction without adversely affecting the reaction.
  • acetonitrile, tetrahydrofuran (THF), MEKdnethyl ethyl ketone (DK), diethyl ethyl formamide (DMF), dimethyl sul foxide (DMS0), methylene chloride (MC), and H 2 O may be used.
  • solvents may be used alone or in combination of two or more.
  • the amount of the solvent is not particularly limited, and may be used in an appropriate amount within a range in which the reaction product is sufficiently dissolved and does not have an unexpected effect on the reaction, and a person skilled in the art may select appropriately.
  • the reaction conditions of the first step are equally applicable to the case where the first step is performed in one step from the original position and in two separate steps.
  • step 12 the intermediate product I of any of Formulas AMI to KM1 is reacted with an alkoxysilane of Formula R2 to alkoxysilylate the hydroxy group at the terminal of the flexible spacer group, thereby providing at least two epoxy groups and at least one An epoxy compound having an alkoxysilyl group via the spacer group according to the present invention having an alkoxysilyl group is obtained. Since the intermediate product I and the alkoxysilane react with each other in the equivalence ratio of the alkylhydroxy group and the alkoxysilane of the intermediate product I according to the stoichiometry, the alkoxysilane of the formula R2 is 0. Intermediate I is reacted with an alkoxysilane of the formula R2 to 1 to 5 equivalents.
  • At least one of 3 ⁇ 4 to 3 ⁇ 4 is a C1-C6 alkoxy group, preferably a C1-C6 alkoxy group, and the rest is a C1-C10 alkyl group,.
  • it is a C1-C5 alkyl group
  • the alkoxy group and the alkyl group may be a straight chain branched chain, may be cyclic or acyclic, at least one selected from the group consisting of N, 0, S, and P It may or may not have a hetero atom.
  • m is an integer of 1-8, Preferably it is an integer of 1-4.
  • the reaction temperature and reaction time of the intermediate product I and the alkoxysilane depend on the reactants. For example, it may be from 1 hour to 72 hours at -20 o C to 120 o C.
  • the reaction can be carried out in the presence of a base if necessary.
  • the reaction proceeds without using a separate base, but the reaction rate is slow, and the reaction rate can be increased by using a base.
  • the base examples include, but are not limited to, K 2 CO 3 , Na 2 CO 3 , HCOs, NaHC0 3 , triethylamine, diisopropylethylamine, and the like. These bases are two kinds of black alone The above can be used together.
  • the base is preferably used in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxy group and / or amine group of the starting material in terms of reaction efficiency.
  • the solvent may optionally be used as necessary.
  • Claim is in step 2, when the viscosity of the reactants at the reaction temperature without the need for solvents suitable for the reaction is in progress, it is "not using the solvent. That is, enough to proceed to the heunhap and stirring of the reaction smoothly in the absence of a solvent, the viscosity of water decreases, it banung not to require a separate solvent, which can 'be determined the person skilled in the art readily.
  • the reactant may be dissolved well, and any aprotic solvent (aprot ic solyent) may be used as long as it can be easily removed after the reaction without any adverse effect on reaction.
  • aprotic solvent aprot ic solyent
  • MEK methyl ethyl ketone
  • DMF dimethyl formamide
  • DMS0 dimethyl sul foxide
  • MC methylene chloride
  • the amount of the solvent to be used is not particularly limited, and may be used in an appropriate amount within a range in which the reactants are sufficiently dissolved and do not adversely affect the reaction, and a person skilled in the art may select appropriately in consideration of this.
  • the semi-funging scheme of an epoxy compound having an alkoxysilyl group via a new spacer group according to the present invention using an epoxy compound of the triphenylmethane core of formula AC is as follows. [Reaction Scheme 1]
  • the epoxy compound having an alkoxysilyl group via the spacer group of the present invention is first described. Introducing at least two narrow groups and at least one flexible spacer group into the starting material (first step), thereafter alkening the hydroxy group at the end of the flexible spacer group (second step) and the alkynyl group It may be prepared by the method by the step of silylation (third step).
  • the first step of Method 2 is the same as the first step of Method 1.
  • the intermediate I obtained in the first step is reacted with an alkene compound of the formula R3 to obtain an intermediate II.
  • the hydroxyl group at the terminal of the flexible spacer group of the intermediate product I reacts with the alkene compound to introduce an alkenyl group.
  • the hydroxyl group (0H) and / or the amine and alkene compound in the core may also be reacted.
  • the alkenyl group of the alkenyl compound of the formula R3 is reacted with 1 equivalent to 1 equivalent of the hydroxy group and / or the amine group of the intermediate product I.
  • the second stage reaction can be carried out in the presence of a base and any solvent.
  • the second step can be reacted for 1 to 120 hours at room temperature to 100 o C in the presence of a base and any solvent.
  • Y is a halide of CI, Br or I, — 0-S0 2 -CH 3 , -0-S0 2 -CF 3 , or -0-
  • m is an integer from 1 to 8, preferably from 1 to 4.
  • J in Formula AM2 is hydrogen, a hydroxyl group, a straight chain of C1 to C10 or; Branched alkyl or C6 to C10 aromatic group,
  • K is a direct linkage, — CH 2 — again;
  • M is Is a linear or branched alkyl group of C1-C10
  • Q is -CH 2 —, -C (CH 3 ) 2- , -C (CF 3 ) 2 —, — S-, -S0 2 _, or
  • each R is independently H or C—C3 alkyl.
  • n is an integer of 2 or more
  • L is lEf, n is an integer of 1 or more
  • n is an integer of 1 or more
  • n is 0 or an integer of 1 or more
  • p is 1 or 2.
  • the upper limit of n value is 1000.
  • the reaction of the second stage reaction is also dependent on the type of reaction and reaction time, for example, reaction at room temperature (eg, 15 ° C. to 25 0 C) to 100 ° C. for 1 to 120 hours.
  • bases that can be used include, but are not limited to, KOH. NaOH, NaH can be mentioned. These bases may be used alone or in combination of two or more of them.
  • the base is preferably used in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxyl group and / or the amine group of the intermediate I in terms of reaction efficiency.
  • the solvent may be optionally used as necessary.
  • the solvent may not be used if the viscosity of the reaction product is suitable for the reaction to proceed at the reaction temperature without a separate solvent in the second step. That is, if the viscosity of the reaction product is low enough that the mixing and stirring of the reaction product can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. If a solvent is used, the possible solvents can dissolve the semiungmul well.
  • Any organic solvent can be used so long as it can be easily removed after the reaction without any adverse effect on the reaction, such as but not limited to acetonitrile, tetrahydrofuran (THF), MEKdnethyl ethyl ketone (DMF), DMF (dimethyl formami de). Dimethyl sul foxide (DMSO), methylene chloride (MC), H 2 O and the like can be used. These solvents may be used alone or in combination of two or more black.
  • the amount of the solvent is not particularly limited and may be used in a suitable amount within a range in which the reaction product is sufficiently dissolved and does not adversely affect the reaction, and those skilled in the art may appropriately select it.
  • the intermediate product of any one of Formulas AM2 to KM2 Alkenyl groups of intermediate II are alkoxysilyl as reaction of II and alkoxysilane.
  • alkoxysilyl having at least two epoxy groups and at least one spacer according to one aspect of the present invention by alkoxysilylating and non-aqueous silylating the alkenyl group of the intermediate II in the presence of a solvent of platinum catalyst and memes.
  • An epoxy compound having a group is obtained.
  • the alkoxyl group of the formula R4 is 0 for 1 equivalent of the alkenyl group of the intermediate II. Repeat intermediate product II with alkoxysilane of formula R4 to 1 equivalent to 5 equivalents.
  • HSiRiR 2 R 3 In the above formula R4, at least one of 3 ⁇ 4 to R 3 is a C1-C6 alkoxy group, preferably a C1-C3 alkoxy group and the rest are independently a C1-C10 alkyl group, preferably a C1-C5 alkyl group.
  • the alkoxy group and the alkyl group may be linear or branched chain, cyclic or acyclic, N. 0, S. And it may or may not have at least one hetero atom selected from the group consisting of P.
  • the reaction temperature £ and reaction time of the intermediate II and the alkoxysilane depend on the reactants, but may be, for example, 1 hour to 72 hours at ⁇ 20 ° C. to 120 ° C.
  • the platinum catalyst is not limited thereto, and for example, a platinum catalyst of Pt0 2 or H 2 PtCl 6 (ChloropIat inic acid) may be used. Platinum catalyst is used in an amount of 4 to 0.05 equivalents of lxlC based on 1 equivalent of alkenyl group of the starting material. It is preferable in terms of reaction efficiency.
  • the solvent may optionally be used as necessary. For example, a solvent may not be used if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without requiring a separate solvent.
  • a separate solvent is not required, which can be easily determined by those skilled in the art.
  • a solvent as a possible solvent, semiamulol can be dissolved well, and any aprotic solvent can be used as long as it can be easily removed after reaction without adversely affecting the reaction.
  • any aprotic solvent can be used as long as it can be easily removed after reaction without adversely affecting the reaction.
  • toluene acetonitrile
  • THF tetrahydrofuran
  • ME methyl ethyl ketone
  • -DMFCdimethyl formami de dimethyl sul foxide
  • MC methylene chloride
  • reaction mixture of an epoxy compound having an alkoxysilyl group via a new spacer group according to the invention using an epoxy compound of the triphenylmethane core of formula AC is as follows:
  • an epoxy composition comprising an epoxy compound having an alkoxysilyl group via a new spacer group provided by any aspect of the present invention.
  • Any composition provided in the present invention is not limited to, for example, for electronic materials. It can be used in various applications such as semiconductor substrates, for example, IC substrates, buildup films, encapsulation materials (packaging materials), printed wiring boards, electronic components, adhesives, paints, composite materials, and the like.
  • any composition provided in the present invention may be a curable composition comprising a curable composition and / or layering agent.
  • Epoxy compositions according to any aspect described above and below of the present invention include epoxy compounds described above in any aspect of the present invention .
  • any type and / or combination of epoxy compositions known in the art is included and which comprises the epoxy composition Hardener, It does not limit the kind and compounding ratio of hardening accelerator crab (catalyst), filler (for example, inorganic particle and / or fiber), other conventional epoxy compound, and other additives.
  • epoxy compositions, cured products and / or. Composites may be used with various kinds of conventional epoxy compounds in terms of property control, depending on their application and / or use. Accordingly, the epoxy compound in the epoxy composition according to any aspect of the present invention described above and below will be via at least one new spacer group selected from the group consisting of the above formulas AF to KF according to one aspect of the invention.
  • epoxy compounds having an alkoxysilyl group hereinafter referred to as 'the present invention and the epoxy compound'
  • any kind of epoxy compound known in the art hereinafter, also referred to as a conventional epoxy compound
  • a conventional epoxy compound any kind of epoxy compound known in the art (hereinafter, also referred to as a conventional epoxy compound) may also be included. .
  • the conventional epoxy compound is not particularly limited and may be any epoxy compound known in the art, for example , a glycidyl ether epoxy compound, a glycidyl epoxy compound, a glycidylamine epoxy compound And at least one selected from the group consisting of glycidyl ester epoxy compounds.
  • the conventional epoxy compound is bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene (f hiorene), anthracene, isocyanurate, triphenylmethane, as a core structure.
  • the epoxy compound of the present invention based on the total weight of the epoxy compound 1 to 100wt% and conventional epoxy compound 0 to 99wt%; For example, seen 10 to 100 wt% of the epoxy compound of the invention and 0 to 90 wt% of the conventional epoxy compound;
  • the epoxy compound of the present invention 30 to 100wt% and the conventional epoxy compound 0 to 70wt%, for example, the epoxy compound of the present invention 50 to 100wt% and the conventional epoxy compound 0 to 50wt%, for example, Epoxy compounds of the invention less than 10 to 100wt and conventional epoxy compounds greater than 0 to 9 (t%; for example, less than 30 to 100wt% of epoxy compounds of the invention and more than 0 to 70wt% of conventional epoxy compounds; for example 50 to less than 100 wt% of epoxy compounds of the present invention and more than 0 to 50% of conventional epoxy compounds.
  • any of the epoxy compositions of the present invention described above and below may further include layering agents (eg, inorganic particles and / or fibers).
  • layering agents eg, inorganic particles and / or fibers.
  • inorganic particles any inorganic particles conventionally known to be used for reinforcing the properties of epoxy resins may be used, including but not limited to silica (eg, including fused silica and crystalline silica), zirconia, titania At least one metal oxide selected from the group consisting of alumina, silicon nitride and aluminum nitride, and at least one selected from the group consisting of silsesquioxane may be used.
  • the inorganic particles may be used alone or in combination of two or more thereof.
  • fused silica can use either a crushed form or a spherical form, it is preferable to use a spherical form in order to raise the compounding quantity of fused silica and to suppress the raise of the melt viscosity of a molding material.
  • the inorganic particles are not limited thereto, but the particle size is 0.5 nm to several tens in consideration of the use of the composite, specifically, the dispersibility of the inorganic particles. Inorganic particles (for example, 50 kPa to 100 kPa) may be used. Since the inorganic particles are dispersed in the epoxy compound, it is preferable to use the inorganic particles of the above sizes due to the difference in dispersibility according to the particle size. In addition, in order to raise the compounding quantity of an inorganic particle, it is preferable to mix
  • the inorganic particles may be suitably added to the epoxy compound according to the appropriate viscosity and the use required for the reduction and application of the CTE of the epoxy composite, and the content of the inorganic particles may be solid content of the epoxy composition. 5 wt% to 95 wt%, for example 5 wt% to 90 wt%, for example 10 wt% to 90 wt%, based on the total weight of the epoxy cured product, 30 wt% to 95 wt%, for example 30 wt% to 90 wt%, for example, 5 wt% to 60 wt%, for example 10 wt% to 50 wt 3 ⁇ 4.
  • the epoxy composition when used as a semiconductor encapsulant or the like, it is not limited thereto, but CTE.
  • the content of the inorganic particles may be, for example, 30 wt% to 95 wt% (for example, based on the total weight of the epoxy cured product in the case of epoxy cured product) relative to the total weight of the solid content of the epoxy composition. 30 wt% to 90%.
  • the content of the inorganic particles in consideration of the CTE value and the strength of the substrate is, for example, based on the weight of the total solid content of the epoxy composition And 5 wt% to 85 wt%, for example, 10 wt% to 80%, based on the total weight of the epoxy cured product.
  • the size of the fiber is not particularly limited, and any kind and size of fibers generally used in the art may be used. have.
  • the fiber is not limited thereto, but any fiber generally used for improving physical properties of the cured epoxy resin may be used. Specifically, glass fibers, organic fibers or mixtures thereof can be used.
  • the term 'glass fiber' as used herein is used to mean not only glass fiber, but also glass fiber fabric, glass fiber nonwoven fabric, and the like.
  • glass fibers include E glass fibers, T glass fibers, S glass fibers, NE glass fibers, D glass fibers, quartz glass fibers, and the like, for example, E or T Glass fiber can be mentioned as an example.
  • E or T Glass fiber can be mentioned as an example.
  • Liquid crystalline polyester fiber, polyethylene terephthalate fiber, wholly aromatic fiber, polybenzoxazole fiber, nylon fiber, polyethylene naphthalate fiber, polypropylene fiber, polyether sulfone fiber, polyvinyl At least one selected from the group consisting of leadenflora fibers, polyethylene sulfide fibers, and polymoether ether ketone fibers may be used alone or in combination of two or more thereof.
  • the fiber content is 10 wt% to 90 wt%, for example 30 wt% to 70 wt%, based, for example, on the total amount of the cured product. , 35wt% to 70 ⁇ %.
  • the resin content may be 10 wt% to 90 wt%, for example, 30 wt% to 70 wt%, and for example, 35 wt% to 70 wt%. It is preferable that the content of the fiber is in the above range in terms of heat resistance improvement and processability.
  • the solid part except the total solidification fiber is normally called a resin component (resin content, R / C). Further, any containing the fibers.
  • the epoxy composition of the present disclosure may further include inorganic particles, if necessary.
  • the inorganic particles may be blended in an amount ranging from 1 wt% to 80 wt% based on the weight of the total resin content in consideration of improvement of physical properties and fairness.
  • the type of inorganic particles that can be used is not particularly limited, any inorganic particles known in the art may be used, for example For example, the above-mentioned kinds of inorganic particles may be used.
  • the epoxy composition of any aspect of the present invention described above and below may further include a curing agent.
  • a curing agent any curing agent generally known as a curing agent for an epoxy compound may be used.
  • the amine curing agent includes aliphatic amines, cycloaliphatic amines and aromatic amines.
  • Other amines and modified polyamines can be used, and amine compounds containing two or more and primary amine groups can be used.
  • amine curing agent examples include 4,4'-dimethylaniline (diamino diphenyl methane) (4,4'-Dimethylani 1 ine (diamino diphenyl methane, DAM or DDM), diamino di.phenylsulfone (diamino di phenyl sulfone (DDS), ' ni_phenylene diamine (m_pheny 1 ene diamine) at least one aromatic amine, diethylene triamine (DETA), diethylene tetramine (diethylene tetramine), Tri ethylene tetraamine (TETA), ni-xylene diamine (MXDA), methane diamine (MDA), N.N'— diethylenediamine (N , N'-diethylenedi amine, ⁇ , ⁇ '-DEDA) eu tetraethylene penta amine (t et r ae t hy 1 en
  • “Menu” at least one member selected from the group consisting of butyl tolylene 0 min (hexamethylenediamine) Aliphatic amines, isophorone diamine (IPDI), N At least one selected from the group consisting of aminoethyl pyrazine (N— Aminoethyl piperazine, AEP), bis (4—amino 3-methylcyclonuxyl) methane (Bis (4-Amino 3-Methylcyclohexyl) Me thane, Larominc 260) And other amines such as cycloaliphatic amines and dicyandiamide (DICY), and modified amines such as polyamides and epoxides.
  • IPDI isophorone diamine
  • N At least one selected from the group consisting of aminoethyl pyrazine (N— Aminoethyl piperazine, AEP), bis (4—amino 3-methylcyclonuxyl) methane (Bis
  • examples of the polyphenol curing agent include phenol novolak resins, cresol novolak resins, and the like. Bisphenol A novolak resin, xylene novolak resin, triphenyl novolak resin, biphenyl novolak resin, dicyclopentadiene novolak resin, naphthalene novolak resin and the like.
  • examples of the acid anhydride curing agent include, but are not limited to, aliphatic acid anhydrides such as dodecenyl succinic anhydride (DDSA), poly azelaic poly anhydride, and nuxahydrophthalic anhydride.
  • trimellitic anhydrides such as (hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride.MeTHPA), methylnaclic anhydride, Trimellitic Anhydride (TMA), pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic acid, aromatic acid anhydrides such as benzophenonetetracarboxylic dianhydride (BTDA), tetrabromophthalic anhydride (tetrabromophthalic anhydride (TBPA), chlorendic anhydride and halogen acid anhydrides such as ide).
  • trimellitic anhydrides such as (hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride.MeTHPA), methylnaclic anhydride, Trimellitic Anhydride (TMA), pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic acid, aromatic acid an
  • the degree of curing of the epoxy composite may be adjusted to the extent of reaction between the curing agent and the epoxy group, and the content of the curing agent may be adjusted based on the concentration of the epoxy group of the epoxy compound according to the desired degree of curing.
  • the content of the curing agent is adjusted so that the epoxy equivalent / amine equivalent ratio is 0.5 to 2.0 and, for example, 0.8 to 1.5. It is preferable to use.
  • the imidazoles described below are also commonly used as curing accelerators, but may also be used as single curing agents.
  • imidazole When imidazole is used as a curing agent, it may be used in an amount of 0.1 to lOphr with respect to the epoxy compound.
  • Any of the epoxy compositions of the present invention described above and below may further comprise optional curing accelerators (curing catalysts) as necessary to promote curing reactions.
  • curing accelerator any catalyst known in the art to be generally used for curing an epoxy composition may be used, but is not limited thereto.
  • imidazole, tertiary amine, fourth Curing accelerators such as quaternary ammonium, organic acid salts, Lewis acids, and phosphorus compounds may be used.
  • dimethyl benzyl amine 2'methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole Imidazoles such as 1- (2-cyano ethyl) -2-alkyl group imidazole and 2-heptadecyl imidazole (heptadecyl imidazol e, 2HDI); Tertiary amine compounds such as benzyl dimethyl amine (BDMA), trisdimethylaminomethyl phenol (DMP-30), diazabicycloundecene (DBU) and triethylenediamine; Quaternary ammonium salts such as tetrabutylammonium bromide; Organic acid salts of DBU; Triphenylphosphine, compounds such as phosphoric ester, BF 3 - monoethylamine (BF 3 - MEA) Rua and the
  • the compounding quantity of the said hardening accelerator is not specifically limited, This It may be used in combination in amounts generally used in the art.
  • the epoxy compound may be 0.1 to 10 phr (part s per hundred resin, parts by weight per 100 parts by weight of epoxy compound), for example, 0.2 to 5 phr.
  • the curing accelerator is preferably used in the above content in terms of curing reaction promoting effect and curing reaction rate control.
  • the epoxy composition is a release agent, surface treatment agent, flame retardant, plasticizer, antimicrobial agent, leveling agent, antifoaming agent, colorant, stabilizer, culling agent, which is conventionally formulated for controlling the physical properties of the epoxy composition, in a range that does not impair the physical properties of the epoxy composition.
  • Other additives such as viscosity modifiers, diluents, rubbers, thermoplastics and the like may also be blended as needed.
  • rubber and / or thermoplastic resins may be added to any epoxy composition of the present invention to make it soluble in any composition according to the present invention.
  • Thermoplastic resins and rubber-modified epoxy resins can be used that are generally known in the art.
  • any rubber known in the art may be used as long as it is not dissolved in the solvent used in the composition and remains dispersed in the composition.
  • These may be used alone or in combination of two or more.
  • the average particle diameter in terms of property improvement is ⁇ .
  • the range of ⁇ ⁇ to 1 is preferable, and the range of 0. zm to 0.6 / ⁇ is more preferable.
  • the rubber particles are, for example, 0.5 wt% in consideration of physical properties based on the weight of the solid content of the epoxy composition.
  • Thermoplastic resins include, but are not limited to, phenoxy resins, Polyvinyl acetal resin. Polyimide resin, polyamideimide resin, polyether sulfone resin, polysulfone resin and the like. These may be used alone or in combination of two or more.
  • the thermoplastic resin may be, for example, 5 wt% to 60 wt% based on the weight of the solid content of the epoxy composition, in consideration of physical properties. Preferably from 3% to 50% by weight.
  • epoxy composition refers to the epoxy compound of the present invention as well as other components constituting the epoxy composition as required, for example, any curing agent, curing accelerator (catalyst), It is understood that fillers (eg, inorganic particles and / or fibers), other conventional epoxy compounds, and other additives may be formulated as needed in the art, other than solvents, and therefore usually solvents in epoxy compositions. May optionally be used to suitably adjust the solids content and / or viscosity of the epoxy composition in view of the processability of the epoxy composition and the like.
  • total weight of solids of the epoxy composition refers to the total weight of the components excluding the component increasing solvent constituting the epoxy composition.
  • the electronic material is not limited thereto, but for example, a substrate, film, prepreg for semiconductor, or a laminated plate in which a metal layer is disposed on a base layer of the composition of the present invention, an encapsulating material (packaging) Materials) as well as electronic components such as printed wiring boards, etc. It can also be applied to various applications such as adhesives, paints, composite materials, etc.
  • any composition comprising the epoxy compound of the present invention An electronic material comprising or consisting of is provided.
  • the semiconductor device comprises a printed wiring board comprising, consisting essentially of or consisting of a composition comprising the epoxy compound of the present invention (eg, a semiconductor Device mounted) It may be a semiconductor device comprising a semiconductor device and / or a semiconductor packaging material.
  • a cured product, adhesive, paint or composite material comprising, consisting essentially of or consisting of any epoxy composition provided in any aspect of the invention.
  • a cured product comprising, consisting essentially of or consisting of the epoxy composition provided in any aspect of the invention described above.
  • the epoxy composition provided in any aspect of the present invention is used as a cured product when it is actually applied, for example, as an electronic material, and includes an epoxy compound and a filler which is an inorganic component in the art.
  • the cured product of the composition is generally referred to as a composite.
  • the epoxy compound provided in one aspect of the present invention exhibits excellent heat resistance properties in the composite and / or excellent flame resistance in the cured product.
  • the composite may have a low CTE, for example 50 ppm / o C or less, for example
  • ppm / ° C or less For example, 30 ppm / o C or less. For example, 15 ppm / ° C or less, for example, 12 ppi / 0 C or less, for example, 10 ppm / o C or less, for example, 8 ppm / 0 C or less.
  • a CTE of 6 ppm / 0 C or less, for example, 4 ppm / 0 C or less is shown. The smaller the CTE value is, the better the physical properties are, and the lower limit of the CTE is not particularly limited. E.g .
  • any epoxy compound according to the invention as an epoxy compound comprising glass fibers as filler, e.g., E-glass and / or T-glass glass fibers, having a resin content of 30 wt% to 60 wt% (resin content of inorganic particles Complex, which may or may not be included), for example, 10 ppm / ° C. or less.
  • 10 ppm / ° C. or less for example, 8 ppm / 0 C or less, for example, 6 ppm / 0 C or less, for example, 4 ppm / ° C or less Represents CTE.
  • any epoxy compound according to the present invention as an epoxy compound, an inorganic particle as a filler for example.
  • Complex comprising 60 to 80wt% of silica particles, for example 70 to 80wt% is, for 50ppm / o C or less, for example, 40ppm / ° C or less, for example, 30 ppm / ° C or less, for example, 20 ppm / ° C or less, for example, 15 ppm / ° C or less, for example. 10 ppm / o C or less.
  • 8 ppm / 0 C or less for example, 6 ppm / ° C or less, for example, 4 ppm / ° C or less, CTE.
  • the composite (cured product containing the filler) of the present invention the Tg is higher than 100 ° C, 'for example, more than 130 ° C, In addition, for example, 250 o C or more or may be less Tg- have.
  • the larger the Tg value, the better the physical properties, and the upper limit of the Tg value is not particularly limited.
  • the epoxy compound self-cured product according to the present invention (cured product containing no layering agent) has a CTE of 50 ppm / o C to 150 ppm / ° C.
  • the value indicated by the range means each including not only the lower limit and the upper limit of the range, but also any lower range between the ranges and all the numbers belonging to the range.
  • C1 to C10 are CI, C2, C3, C4, C5, C6, C7. . C8. It is understood to include both C9 and C10.
  • the lower limit value or the upper limit value of the numerical range is not specified, and the smaller or larger the numerical value is, the more preferable.
  • a CTE of 4 ppm / 0 C or less is 4, 3.5, 3, 2.7, 2 ,. It is understood to include all values in the range 1.4, 1, 0.5 ppm / ° C, and the like.
  • (2) second step: alkoxysilylation 10 g of the intermediate product synthesized in the first step and THF were added to the two-necked flask and stirred. After that . 5.2 g of 3- (triethoxysilyl) propyl isocyanate and 2.7 g of diisopropylethylamine were added thereto and reacted at 65 0 C for 12 hours. After completion of reaction, purification was performed using ethyl acetate and nucleic acid. After removing the nucleic acid layer as a supernatant and completely drying it using a vacuum pump, an epoxy compound having a silyl group having [epoxy group]: [alkoxysilyl group] 2: 1 was obtained.
  • Step 1 reaction to react the alkylhydroxy compound and epichlorohydrin to produce intermediate product I and step 2 reaction to react with alkoxysilane were carried out, and the concentration ratio of [epoxy group] to [alkoxysilyl group] was 3: 1.
  • Phosphorus epoxy compound was obtained.
  • the amount of reactants used in each synthesis step is shown in Table 1 below.
  • Step 1 reaction to react the alkyl hydroxy compound and epichlorohydrin to produce intermediate product I and step 2 reaction to react with alkoxysilane were carried out so that the concentration ratio of [epoxy group]: [alkoxysilyl group] was 2: 1.
  • An epoxy compound was obtained.
  • the amount of reactants used in each synthesis stage "shown in the table below.
  • Step 1 ⁇ R
  • the reaction of epichlorohydrin was carried out to react the first step of reacting with the intermediate product I and the two-step reaction of reacting with an alkoxysilane to obtain an epoxy compound having a concentration ratio of 4: 1 to an epoxy group: alkoxysilyl group.
  • the amount of reactants used in each synthesis step is shown in the table below.
  • Step 1 ⁇ R
  • Step 1 ⁇ R
  • Step 1 ⁇ R
  • crab step 1 introduction of spacer group and epoxy group
  • the flask was charged with 10 g of intermediate II synthesized in the second step, 88 mg of Pt0 2 , 3.3 ⁇ 4 trisilane silane, and 250 ml of toluene and stirred at room temperature for 5 minutes. Thereafter, the reaction was carried out for 12 hours at a temperature of 80 ° C., and then filtered through a celite filter to remove the inorganic material. By evaporating and drying, toluene was removed and completely dried using a vacuum pump to obtain an epoxy compound having an epoxy group: alkoxysilyl group ratio of 2: 1.
  • a glass fiber composite was prepared by immersing glass fiber (Nittobo glass fiber (Nittobo glass fiber fabric, T-glass)) in the epoxy mixture. The composite was then placed in a vacuum oven heated to 100 ° C. It removed and hardened
  • an epoxy compound, a silica slurry (dispersion solution: methyl ethyl ketone solvent, silica average size 1) and polyvinyl acetal are dissolved in ⁇ , ⁇ -dimethylacetamide so that the solid content is 40%.
  • curing agent was added and it mixed for further 30 minutes.
  • the mixture was placed in a vacuum oven heated to 100 ° C. and the solvent was removed to cure to obtain an epoxy filler (inorganic particle) composite (5 (m ′′ ⁇ 5 ⁇ X 3 ′).
  • the composites of Examples 1 to 10 not only show low CTE but also show no glass transition degree compared to the composites of Comparative Examples 1 and 2 (Tg-ess, TgL) and heat resistance were found to be improved.

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Abstract

La présente invention concerne un nouveau composé époxy comportant un espaceur entre un noyau et un groupe alcoxysilyle, son procédé de préparation, une composition le contenant, un produit durci, et son utilisation. Le composé époxy selon l'invention présente d'excellentes caractéristiques de résistance à la chaleur, en particulier un bas coefficient de dilatation thermique et une température de transition vitreuse élevée (qui comprend une forme Tg-moins qui ne manifeste pas de température de transition vitreuse), et une fragilité améliorée dans un composite et/ou présente d'excellentes propriétés ignifuges dans un produit durci. L'invention concerne : un composé époxy ayant un groupe alcoxysilyle qui est passé par un groupe espaceur qui comporte au moins deux groupes époxy, au moins un groupe alcoxysilyle, et un nombre prédéfini d'atomes d'hydrogène, de groupes hydroxy et/ou de groupes alcényle ; un procédé de préparation du composé époxy au moyen d'une étape d'introduction d'un groupe espaceur et d'un groupe époxy et d'une étape d'alcoxylation ; un procédé de préparation du composé époxy au moyen d'une étape d'introduction d'un groupe espaceur et d'un groupe époxy, d'une étape d'alcénylation et d'une étape d'alkoxysilylation ; une composition le contenant ; et un produit durci et son utilisation. La composition époxy comprenant un composé époxy ayant un groupe alcoxysilyle qui est passé par un groupe espaceur selon l'invention présente des caractéristiques de résistance à la chaleur améliorées, à savoir des effets de réduction du CTE, d'accroissement de la température de transition vitreuse ou ne manifestant pas de température de transition vitreuse (ci-après désigné "Tg moins"') dans un composite. La composition époxy présente en outre une fragilité améliorée. De plus, le produit durci obtenu à partir de la composition époxy comprenant le composé époxy ayant un groupe alcoxysilyle qui est passé par un groupe espaceur selon l'invention présente d'excellentes caractéristiques ignifuges dues à l'introduction du groupe alcoxysilyle.
PCT/KR2015/002138 2014-03-05 2015-03-05 Composé époxy ayant un groupe alcoxysilyle, son procédé de préparation, composition le contenant, produit durci, et son utilisation WO2015133840A2 (fr)

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KR1020150028082A KR101749551B1 (ko) 2014-03-05 2015-02-27 알콕시실릴기를 갖는 에폭시 화합물, 이의 제조 방법, 이를 포함하는 조성물, 경화물 및 이의 용도

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KR101596880B1 (ko) * 2012-09-17 2016-02-23 한국생산기술연구원 알콕시실릴기를 갖는 에폭시 화합물, 이의 제조 방법, 이를 포함하는 조성물, 경화물 및 이의 용도
JP6153631B2 (ja) * 2013-02-25 2017-06-28 コリア インスティチュート オブ インダストリアル テクノロジー アルコキシシリル基を有するエポキシ化合物、その製造方法、それを含む組成物と硬化物及びその用途

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