Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/07—Parts immersed or impregnated in a matrix
  • B32B2305/076—Prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
  • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to the field of packaging materials for electronic products, and more particularly to an epoxy-modified acrylate resin composition and a prepreg, a laminate, and a metal foil-clad laminate prepared using the same.
• High-density packaging becomes a solution, such as POP packaging (package stacking technology), MCP package (multi-chip package), 2.5D & 3D package (3D package). Due to the increased packing density, the requirements for mountability and connectivity are higher, and the low warpage of the package carrier (here specifically referred to as the package substrate) is particularly important. In order to achieve low warpage, it is a well-known solution to suppress warpage by high rigidity, but as the complexity of the package increases, the degree of warpage of different parts is different, which causes excessive stress in the package and causes the circuit to fail. At the time, high rigidity becomes a hidden danger of reducing package reliability.
• Patent Document 1 Patent Document 2, Patent Document 3, and Patent Document 4 disclose a solution for suppressing warpage by low rigidity, which achieves low warpage by low rigidity and low coefficient of thermal expansion (CTE). .
• CTE coefficient of thermal expansion
• Patent Document 1 application number: 201380003638.4;
• Patent Document 2 Application No.: 201510100415.0;
• Patent Document 3 Application No.: 201510137022.7;
• Patent Document 4 Application No.: 201610409104.7.
• the known technical means for achieving low rigidity are mainly the increase of the soft segment in the resin and the addition of the elastomer, but this tends to increase the viscosity of the resin, lower the polarity of the resin, and cause the dispersion of the inorganic filler to be deteriorated.
• the interlayer adhesion of the prepared laminate and the bonding strength with the metal foil are lowered, eventually causing deterioration of heat resistance of the package substrate, deterioration of moist heat resistance, and severe deterioration of package reliability.
• An object of the present invention is to provide an epoxy-modified acrylate resin composition
• an inorganic filler modified with a specific silane coupling agent, and a prepreg, a laminate, and a metal foil-clad laminate prepared therefrom have good properties. Heat resistance, heat and humidity resistance, and low coefficient of thermal expansion and modulus are suitable for high-end packaging.
• the present invention adopts the following technical means:
• One aspect of the present invention provides an epoxy-modified acrylate resin composition
• an epoxy-modified acrylate resin composition comprising an epoxy-modified acrylate resin (A) and a silane having a structure of the formula (I)
• B surface-treated inorganic filler
• D epoxy resin
• E cyanate resin
• F bismaleimide resin
• each segment is randomly random, a, b, c and d are molar fractions, a+b+c+d ⁇ 1, 0.10 ⁇ a ⁇ 0.90, 0.01 ⁇ b ⁇ 0.50, 0 ⁇ c ⁇ 0.70, 0 ⁇ d ⁇ 0.90, wherein R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, and R 2 is a terminally substituted epoxy group or maleic acid An alkyl group substituted with an amine group and having a carbon number of 20 or less, and X is a linear or branched alkyl group having 20 or less carbon atoms.
• the number average molecular weight of the silane coupling agent (B) having the structure of the formula (I) is from 3,000 to 12,000.
• the content of the silane coupling agent (B) having the structure of the formula (I) is from 1 to 10% by mass, preferably from 2 to 5% by mass, based on 100% by mass of the total content of the inorganic filler (C).
• the epoxy-modified acrylate resin (A) has the structure of formula (II):
• each segment is random, k, l, m and n are molar fractions, k+l+m+n ⁇ 1, 0 ⁇ k ⁇ 0.30, 0.01 ⁇ l ⁇ 0.20, 0.10 ⁇ m ⁇ 0.60, 0 ⁇ n ⁇ 0.60, wherein R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom or an alkyl group having 1-8 carbon atoms, and R 7 is Ph (phenyl), -COO(CH 2 ) 2 Ph or COOCH 2 Ph.
• the R 3 , R 4 , and R 6 are each independently a hydrogen atom or a methyl group; and the R 5 is an alkyl group of 1 to 8 carbon atoms.
• the epoxy-modified acrylate resin (A) has a weight average molecular weight of 100,000 or more and 850,000 or less, more preferably a weight average molecular weight of 100,000 or more and 450,000 or less, and still more preferably a weight average molecular weight of 100,000. More preferably, it is 250,000 or less, and it is more preferable that the weight average molecular weight is 100,000 or more and 200,000 or less.
• the epoxy-modified acrylate resin (A) has an epoxy value of 0.10 eq/kg or more and 0.80 eq/kg or less.
• the content of the epoxy-modified acrylate resin (A) is relative to the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). 100% by mass is 5 to 60% by mass.
• the content of the inorganic filler (C) is 10% by mass based on 100% by mass of the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). ⁇ 300% by mass, preferably 30 to 270% by mass, and more preferably 50 to 250% by mass.
• the epoxy resin (D) content is 20-80% relative to the total content of the epoxy resin (D), cyanate ester (E), and bismaleimide (F);
• the mass% is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
• the content of the cyanate resin (E) is 100% by mass relative to the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). It is 15 to 70% by mass, preferably 20 to 60% by mass, and more preferably 20 to 50% by mass.
• the content of the bismaleimide resin (F) is relative to the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). 100% by mass is 5 to 50% by mass, preferably 10 to 40% by mass.
• Another aspect of the present invention provides a prepreg comprising a substrate and the above epoxy-modified acrylate resin composition attached to the substrate by dipping or coating.
• Another aspect of the invention provides a laminate comprising at least one of the above prepregs.
• Another aspect of the present invention provides a metal foil-clad laminate comprising at least one of the above prepreg and a metal foil coated on one or both sides of the prepreg.
• the epoxy-modified acrylate resin composition provided by the present invention, the epoxy-modified acrylate as an elastomer can reduce the rigidity of the package substrate, and the negative expansion characteristic at a high temperature reduces the thermal expansion coefficient of the package substrate, and (I) Structure of the silane coupling agent (B) Surface treatment of the inorganic filler, so that the inorganic filler has excellent dispersibility in the epoxy-modified acrylate, and improves the interlayer adhesion of the laminate due to the decrease in the polarity of the resin And a problem that the bonding strength with the metal foil is lowered, the prepreg, the laminate, and the metal foil-clad laminate prepared using the resin composition have good heat resistance, moist heat resistance, and low coefficient of thermal expansion and modulus, and The interlayer adhesion of the laminate and the bonding strength with the metal foil are suitable for high-end packaging.
• the epoxy-modified acrylate resin composition of the present invention comprises an epoxy-modified acrylate resin (A), an inorganic filler (C) surface-treated with a silane coupling agent (B), an epoxy resin (D), and cyanic acid.
• each component will be described in detail.
• the epoxy-modified acrylate resin (A) may have a structure of the formula (II).
• each segment is random, k, l, m and n are molar fractions, k+l+m+n ⁇ 1, 0 ⁇ k ⁇ 0.30, 0.01 ⁇ l ⁇ 0.20, 0.10 ⁇ m ⁇ 0.60, 0 ⁇ n ⁇ 0.60, wherein R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom or an alkyl group having 1-8 carbon atoms, and R 7 is Ph (phenyl), -COO(CH 2 ) 2 Ph or COOCH 2 Ph.
• the epoxy-modified acrylate resin (A) may have a weight average molecular weight of 100,000 or more and 850,000 or less, more preferably a weight average molecular weight of 100,000 or more and 450,000 or less, and still more preferably a weight average molecular weight of 100,000 or more and 250,000. In the following, it is more preferable that the weight average molecular weight is 100,000 or more and 200,000 or less, and it is characterized by an elastomer.
• the weight average molecular weight of the epoxy-modified acrylate resin (A) is limited, and if the weight average molecular weight of the epoxy-modified acrylate resin (A) is 850,000 or more, the epoxy-modified acrylate resin (A) cannot Completely dissolved in the resin composition and layered; further defined, the epoxy-modified acrylate resin (A) has a weight average molecular weight of not more than 450,000, and the epoxy-modified acrylate resin (A) can be completely dissolved in the resin In the composition; furthermore, the epoxy-modified acrylate resin (A) has a weight average molecular weight of not more than 250,000, and the epoxy-modified acrylate resin (A) has excellent wettability with the substrate; , the epoxy-modified acrylate resin (A) has a weight average molecular weight of not more than 200,000, and the epoxy-modified acrylate resin (A) has good compatibility with other combinations of the resin composition, and is avoided in the resin composition.
• the epoxy-modified acrylate resin (A) may have an epoxy value of 0.10 eq/kg or more and 0.80 q/kg or less, and the epoxy-modified acrylate resin (A) and the epoxy resin (D) and cyanic acid are ensured.
• the ester resin (E) and the bismaleimide resin (F) have good compatibility, and the epoxy-modified acrylate resin (A) exists in a phase state of microphase separation in the resin composition, and exhibits a reduced mode. The amount and the effect of the XY coefficient of thermal expansion, and does not affect the heat resistance and heat and humidity resistance of the prepreg, the laminate, and the metal foil-clad laminate.
• the content of the epoxy-modified acrylate resin (A) may be 100% by mass based on the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). It is 5 to 60% by mass.
• the content of the epoxy-modified acrylate resin (A) is more than 60% by mass, the viscosity of the resin composition in the varnish state may be excessively large, which may affect the dispersion effect of the inorganic filler (C).
• the epoxy-modified acrylate resin (A) does not affect the uniform dispersion of the inorganic filler (C) in the resin composition, and it is not necessary to have a formula (I) Structure of silane coupling agent (B) Modified inorganic filler (C).
• epoxy-modified acrylate resin (A) having the structure of the formula (II) may be selected as long as the compatibility with the resin composition is good and the heat resistance to the laminate is good.
• the acrylate resin which has no adverse effect on the heat and humidity resistance can be selected.
• the structure of the epoxy-modified acrylate resin (A) is limited only to clarify the selection principle of the epoxy-modified acrylate resin.
• the inorganic filler (C) can improve heat resistance and moist heat resistance of the resin composition and the laminate, and can also improve the dimensional stability of the laminate and the metal foil-clad laminate and lower the coefficient of thermal expansion.
• the surface-treated inorganic filler (C) is easily agglomerated, and a surface treatment agent such as a silane coupling agent can improve the situation.
• a surface treatment agent such as a silane coupling agent
• Commonly used silane coupling agents include vinyl trimethoxysilane and vinyl triethoxysilane.
• silane coupling agents are small molecules, and there are no segments which are similarly compatible with the epoxy-modified acrylate resin (A), and the inorganic filler (C) modified by these silane coupling agents is modified with epoxy.
• the acrylate resin (A) has poor adhesion and affects the dispersibility of the inorganic filler (C) in the epoxy-modified acrylate resin (A).
• the inorganic filler (C) is surface-treated with a silane coupling agent (B) having a structure of the formula (I) or a silane coupling agent (B) having a structure of the formula (I) is directly added to the resin composition.
• the silane coupling agent (B) has the structure of the formula (I), and the formula (I) contains four different segments, each of which is randomly random, a, b, c and d are molar fractions, a+b+ c+d ⁇ 1, 0.10 ⁇ a ⁇ 0.90, 0.01 ⁇ b ⁇ 0.50, 0 ⁇ c ⁇ 0.70, 0 ⁇ d ⁇ 0.90, wherein R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms R 2 is an alkyl group in which a terminal group is substituted with an epoxy group or a maleimide group and has a carbon number of 20 or less, and X is a linear or branched alkyl group having 20 or less carbon atoms.
• each segment of the silane coupling agent (B) is defined to ensure a strong bridging action of the silane coupling agent (B) in the epoxy-modified acrylate resin composition.
• the silane coupling agent (B) must contain a butadiene segment a in addition to the silane-containing segment b, thereby ensuring a higher non-polar segment n with the epoxy-modified acrylate resin (A). Compatibility, while reacting with the surface of the inorganic filler (C) or the hydroxyl groups in the resin to form a bridge between the resin compositions.
• the silane coupling agent (B) may further contain a styrene segment c and a segment d in which the side chain terminal is substituted with an epoxy group or a maleimide group, further improving the compatibility of the inorganic filler (C) with the resin composition. It does not adversely affect other properties of the resin composition. Modification of the inorganic filler (C) with a silane coupling agent (B) can significantly improve the compatibility of the inorganic filler (C) with the epoxy-modified acrylate resin composition, thereby improving the inorganic filler (C) in the epoxy Dispersibility in the modified acrylate resin composition.
• the polarity of the silane coupling agent (B) is lowered, and the compatibility with the epoxy-modified acrylate resin composition is deteriorated, resulting in deterioration of properties of the laminate, such as mechanical properties, etc.; >0.50, the polarity of the silane coupling agent (B) rises, the compatibility with the epoxy-modified acrylate resin (A) is deteriorated, and the water absorption of the resin composition is improved, which ultimately affects the durability of the laminate. Moist heat and heat resistance.
• the number average molecular weight of the silane coupling agent (B) is 3,000 or more and 12,000 or less.
• the molecular weight of the silane coupling agent (B) is limited, and if the number average molecular weight is less than 3,000, the polarity of the silane coupling agent (B) is high, and the inorganic filler (C) modified with the silane coupling agent (B) Can not be uniformly dispersed in the epoxy-modified acrylate resin (A), and causes the peel strength of the laminate to decrease; if the number average molecular weight is higher than 12,000, the silane coupling agent (B) is non-polar, and epoxy
• the compatibility of the resin (D), the cyanate resin (E), and the bismaleimide resin (F) is poor, and in the resin composition in the varnish state, the segment b of the silane coupling agent (B) is Non-reactive long-chain encapsulation does not effectively modify the inorganic filler (C).
• the amount of the silane coupling agent (B) may be from 1 to 10% by mass, preferably from 2 to 5% by mass, based on 100% by mass of the total content of the inorganic filler (C) to ensure a modification effect.
• the amount of the silane coupling agent (B) is limited. If the amount is too high, the free silane coupling agent is precipitated during the heat curing process, which affects the peel strength, heat resistance and heat and humidity resistance; if the amount is too low, then The modification effect of the inorganic filler (C) is poor.
• the type of the inorganic filler (C) is not limited and may be selected from silica (including crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica), metal hydroxide (including aluminum hydroxide, magnesium hydroxide), boehmite, metal oxides (including aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, molybdenum oxide), aluminum nitride, silicon nitride, silicon carbide, molybdic acid Zinc, zinc borate, zinc stannate, barium sulfate, barium titanate, talc, mica, glass powder (including E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass) One or more of powder, quartz glass powder, short glass fiber or hollow glass.
• silica including crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica
• metal hydroxide
• crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, hydrogen are preferred.
• alumina, magnesium hydroxide, boehmite, alumina, magnesia, aluminum nitride, silicon nitride, and silicon carbide are more preferably spherical fused silica.
• the content of the inorganic filler (C) may be 10 to 300% by mass based on 100% by mass of the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). It is preferably 30 to 270 mass%, more preferably 50 to 250 mass%.
• the epoxy resin (D) is selected from the group consisting of organic compounds having at least two epoxy groups in a molecular structure, and may be selected from bisphenol A type epoxy resins and bisphenol F.
• the epoxy resin of the present invention is further preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type.
• Epoxy resin, naphthol novolac type epoxy resin, bismuth type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl phenolic type epoxy resin, in the molecule Any one or a mixture of at least two kinds of epoxy resins having an arylene ether structure, particularly preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, a fluorene type ring Any one or a mixture of at least two of an oxyresin, a phenolphthalein type epoxy resin, an aralkyl novolac type epoxy resin, and an epoxy resin having an arylene ether structure in its molecule.
• R 7 , R 8 , R 9 and R 10 in the formula (III) are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and x is a natural number of 20 or less.
• R 11 in (IV) is a hydrogen atom, a methyl group or an ethyl group;
• the epoxy resin (D) contains a biphenyl type epoxy resin having a structure of the formula (III)
• the content of the biphenyl epoxy resin of the formula (III) is 0% by mass relative to the total content of the epoxy resin (D). ⁇ 80% by mass, preferably 0 to 60% by mass, to ensure good compatibility of the epoxy-modified acrylic resin (A) in the resin composition, and this limitation is applicable not only to the biphenyl ring having the structure of the formula (III) Oxygen resin, other epoxy resins containing biphenyl structure are suitable.
• the content of the epoxy resin (D) may be 20 to 80% by mass based on 100% by mass of the total content of the epoxy resin (D), the cyanate ester (E), and the bismaleimide (F). It is 30 to 70% by mass, and more preferably 40 to 60% by mass.
• the cyanate resin (E) is a thermosetting resin component in the resin composition of the present invention, and when used in combination with the epoxy resin (D), the adhesion of the resin composition, particularly the adhesion to the metal foil, can be improved.
• the cyanate resin (E) may be selected from a cyanate monomer or a cyanate prepolymer having at least two cyanate groups in a molecular structure selected from the group consisting of bisphenol A type cyanate resin and novolac type cyanide.
• Acid ester resin naphthol type cyanate resin, naphthol novolac type cyanate resin, dicyclopentadiene type cyanate resin, aralkyl type cyanate resin, aralkyl novolac type cyanate resin, Bisphenol A type cyanate prepolymer, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type cyanate One or more of a prepolymer, an aralkyl type cyanate prepolymer or an aralkyl novolac type cyanate prepolymer.
• the content of the cyanate resin (E) in the epoxy-modified acrylate resin composition is defined, and optionally, the content of the cyanate resin (E) is relative to the epoxy resin (D), cyanate ester
• the total content of the resin (E) and the bismaleimide resin (F) is from 15 to 70% by mass, preferably from 20 to 60% by mass, and more preferably from 20 to 50% by mass. If the content of the cyanate resin (E) is more than 70% by mass, the water absorption of the laminate is improved due to the introduction of the polar group cyanate group, and the heat and humidity resistance is deteriorated, and the content of the cyanate resin (E) is low. At 15% by mass, the dielectric properties of the laminate are lowered due to a decrease in the content of the triazine ring of the cyanate ester-based self-polymerization product, and the glass transition temperature is lowered.
• the bismaleimide resin (F) is more excellent in the mechanical properties, heat resistance, and planar thermal expansion coefficient of the resin composition.
• the kind of the bismaleimide resin (F) is not particularly limited, and may be selected from compounds having at least one maleimide group in a molecular structure, and preferably contains at least two maleimides in a molecular structure.
• the compound of the group may be selected as long as it has good compatibility with the epoxy resin (D) and the cyanate resin (E) and has good solubility in an organic solvent, and is further preferably selected from N-phenyl horse.
• the content of the bismaleimide resin (F) may be 5% by mass based on 100% by mass of the total content of the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F). ⁇ 50% by mass, preferably 10 to 40% by mass.
• the epoxy-modified acrylate resin composition of the present invention may also be added with an accelerator as needed to ensure complete curing.
• Promoters capable of promoting self-polymerization of cyanate resin and ring-opening reaction of epoxy resin such as organic salts of metals such as copper, zinc, cobalt, nickel, manganese, imidazole and its derivatives, tertiary amines, etc.
• organic salts of metals such as copper, zinc, cobalt, nickel, manganese, imidazole and its derivatives, tertiary amines, etc.
• it contains at least an organic salt of a metal such as copper, zinc, cobalt, nickel or manganese.
• the amount of the accelerator is based on the gelation time (GT) of the epoxidized epoxy-modified acrylate resin composition, and the GT is controlled to be 200 to 500 s in order to ensure processability.
• GT gelation time
• the resin composition of the present invention may further contain various additives such as a flame retardant, a heat stabilizer, and light stability as needed.
• additives such as a flame retardant, a heat stabilizer, and light stability as needed.
• Agents, antioxidants, lubricants, etc. are not limited, and are based on specific use requirements.
• the epoxy-modified acrylate resin composition of the present invention can be obtained by dissolving, mixing, stirring, and dispersing the epoxy-modified acrylate resin (A) through the surface of the silane coupling agent (B) having the structure of the formula (I).
• the inorganic filler (C), the epoxy resin (D), the cyanate resin (E), and the bismaleimide resin (F) are treated to prepare.
• the inorganic filler (C) surface-treated by the silane coupling agent (B) having the structure of the formula (I) may be prepared by dissolving a silane coupling agent (B) having a structure of the formula (I) in a solvent, and adding an inorganic filler. (C) after dispersion.
• the dispersing device may be a ball mill, a sand mill, a high pressure homogenizer, or the like, as long as the inorganic filler can be dispersed in a submicron order.
• an organic solvent to dissolve the resin, as long as the various resins can be completely dissolved, and separation does not occur when mixed, such as methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone, Toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, ethyl acetate or the like may be used.
• One or more solvents may be used.
• the prepreg of the present invention is formed of a semi-cured epoxy-modified acrylate resin composition and a substrate.
• the prepreg is formed by immersing the epoxy-modified acrylate resin composition in a varnish state to wet the solvent and converting it into a semi-cured state.
• the substrate of the present invention is not particularly limited, and is usually a glass fiber cloth, and the material may be inorganic fibers (for example, E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz, etc.) or Organic fibers (for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.) are preferably E glass fiber cloth.
• inorganic fibers for example, E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz, etc.
• Organic fibers for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.
• the laminate of the present invention comprises at least one of the above prepregs.
• the metal foil-clad laminate of the present invention comprises at least one of the above prepreg and a metal foil coated on one or both sides of the prepreg.
• a metal foil-clad laminate can be produced by laminating 1 to 20 prepregs and laminating a metal foil such as copper or aluminum on one or both sides thereof.
• the examples and the comparative examples are different only in the type of the raw materials to be used, and the preparation processes of the resin composition and the prepreg, the laminate, and the metal foil-clad laminate obtained using the same are the same, and therefore, the description will be made without distinction.
• each component was calculated as a solid matter.
• Epoxy-modified acrylate resin (A), epoxy resin (D), cyanate resin (E), bismaleimide resin (F), organic metal salt promoter and imidazole accelerator The mass parts shown in Table 2 were mixed, dissolved and diluted with dimethylformamide and methyl ethyl ketone, and uniformly mixed, and then the inorganic filler (C) modified with the silane coupling agent (B) having the structure of the formula (I) was added and mixed. After homogenization, it was dispersed by a sand mill, the number of revolutions was set to 2,500 rpm, and sanding was performed twice to prepare an epoxy-modified acrylate resin composition in a varnish state.
• the silane coupling agent of the formula (I) (B) is a specific method of modifying the inorganic filler (C) by dissolving the silane coupling agent (B) having the structure of the formula (I) in accordance with the mass parts shown in Table 2.
• inorganic filler (C) stir well, disperse with sand mill, sanding cycle for 10 minutes, seal at room temperature for 5 days, shake well before use.
• the epoxy-modified acrylate resin composition in the varnish state is infiltrated with Nippon Textile 2116 glass fiber cloth, and is dried by heating in a blast oven at 155 to 165 ° C for 7 to 8 minutes to modify the epoxy in the varnish state.
• the acrylate resin composition was converted into a resin composition in a semi-cured state, and the thickness was controlled to 130 to 140 ⁇ m, thereby producing a prepreg.
• Two sheets and eight sheets of the above prepreg were respectively laminated, and electrolytic copper foils each having a thickness of 35 ⁇ m were coated on both sides thereof, and solidified in a press at a curing pressure of 45 kg/cm 2 and a curing temperature of 220 ° C.
• a copper-clad laminate having a thickness of about 0.35 mm and 1.1 mm was obtained in 1 to 2 hours.
• the laminate prepared by using the resin composition of the present invention and the metal foil-clad laminate are tested for heat resistance (Tg, T300), heat and humidity resistance, peel strength, interlayer adhesion, warpage, and bending strength. And the XY coefficient of thermal expansion (CTE), and the uniformity of dispersion and distribution of the inorganic filler in the resin by scanning electron microscopy, and the test results are further illustrated and described in the following examples.
• the test method is as follows:
• DMA dynamic mechanical thermal analyzer
• T300 with copper measured by thermal analysis mechanical method (TMA), the heating rate is 10 °C / min, the result is the time of the curve mutation at 300 °C, the unit min, if more than 60min, the result is 60min, the sample size is 6.5mm*6.5 Metal foil laminate of mm*1.1mm.
• TMA thermal analysis mechanical method
• a sample strip having a metal foil width of 3.0 mm was prepared by etching on a sample by using a tape or other means, and a stripper was applied in a vertical direction by applying a pressure to the metal foil to peel the laminate at a speed of 50 mm/min.
• Interlayer adhesion Vertical separation method, a strip of 100mm*3.0mm*0.5mm is prepared in the center of the sample (longitudinal direction), and two layers of prepreg are stripped at one end and fixed in anti-stripping. On the instrument pressing device, a pressure was applied in the vertical direction to peel the metal foil from the laminate at a speed of 50 mm/min, the unit was N/mm, and the sample size was 150 mm*50 mm*1.0 mm, and the length direction was the warp direction.
• Flexural modulus A laminate measured by a material testing machine with a span of 25.4 mm, a test speed of 0.76 mm/min, a unit of GPa, and a sample size of 76.2 mm * 25.4 mm * 1.0 mm.
• XY-direction thermal expansion coefficient measured by thermal analysis mechanical method (TMA), the heating rate is 10 ° C / min, the temperature is raised from room temperature to 300 ° C, and the temperature is raised twice. After the first temperature rise, the temperature is cooled to room temperature, and then the sample is discharged again.
• TMA thermal analysis mechanical method
• the temperature is increased twice, and the second step is to increase the coefficient of thermal expansion in the plane direction from 50 ° C to 130 ° C, the unit is ppm / ° C, the sample size is 60 mm * 4 mm * 0.25 mm, the direction of the glass warp yarn is X direction, glass fiber The weft direction was in the Y direction, and the sample was baked in an oven at 105 ° C for 1 hour and then cooled to room temperature in a desiccator.
• the resin composition of the present invention uses the silane coupling agent (B) having the structure of the formula (I) to modify the inorganic filler (C) without affecting the heat resistance and heat and humidity resistance of the laminate.
• the silane coupling agent (B) having the structure of the formula (I) to modify the inorganic filler (C) without affecting the heat resistance and heat and humidity resistance of the laminate.
• the interlayer adhesion of the laminate and the peel strength of the metal foil-clad laminate can be effectively improved and can be improved.
• the Tg and modulus of the laminate at the same time, help to further reduce the XY coefficient of thermal expansion of the laminate, suitable for high-end packaging.
• Example 4 Comparing Example 4, Example 5, and Example 6, it can be seen that the copper-clad laminate prepared by the resin composition has good heat resistance, heat and humidity resistance, and low coefficient of thermal expansion and modulus.
• the 20,000-molecular weight epoxy-modified acrylate resin (A) has better adhesion.

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