WO2021128630A1 - 热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板 - Google Patents

热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板 Download PDF

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Publication number
WO2021128630A1
WO2021128630A1 PCT/CN2020/082466 CN2020082466W WO2021128630A1 WO 2021128630 A1 WO2021128630 A1 WO 2021128630A1 CN 2020082466 W CN2020082466 W CN 2020082466W WO 2021128630 A1 WO2021128630 A1 WO 2021128630A1
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WIPO (PCT)
Prior art keywords
epoxy resin
parts
resin composition
component
thermosetting epoxy
Prior art date
Application number
PCT/CN2020/082466
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English (en)
French (fr)
Inventor
陈勇
许永静
唐国坊
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to KR1020227025007A priority Critical patent/KR20220119107A/ko
Priority to US17/787,424 priority patent/US20230045615A1/en
Publication of WO2021128630A1 publication Critical patent/WO2021128630A1/zh

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5377—Phosphinous compounds, e.g. R2=P—OR'
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the invention belongs to the technical field of printed circuit boards, and specifically relates to a thermosetting epoxy resin composition and a prepreg, laminate and printed circuit board using the thermosetting epoxy resin composition.
  • optical semiconductors represented by LEDs have been used in display applications, movable devices, backlights for mobile phones, sensors, and automotive components.
  • laminates/metal-clad laminates used in printed circuit boards for LED mounting are required to have excellent light resistance, especially high whiteness after high temperatures.
  • the flame retardant performance and dimensional stability of laminates/metal-clad laminates are also increasingly stringent.
  • CN 109181604A Use bisphenol A/bisphenol F epoxy resin, methyl tetrahydrophthalic anhydride or Nadic acid anhydride, catalyst to obtain highly transparent epoxy resin glue, but this combination is not flame retardant and is not used for prepreg and Laminate.
  • CN 108641650A discloses the use of bisphenol F epoxy, carboxy-terminated butyl rubber, diaminodiphenyl sulfone, imidazole, surfactant, alumina, boron nitride, and ethylene glycol methyl ether for LED circuit epoxy resin glue,
  • this system does not have high whiteness, and has poor thermal discoloration resistance after high temperature treatment.
  • CN 103459493A uses bisphenol A skeleton epoxy resin, cycloaliphatic epoxy resin, aromatic polycarboxylic acid anhydride or partially hydrogenated anhydride, titanium dioxide and dispersant to prepare resin composition to achieve high peel strength and heat treatment After the purpose of high reflectivity, but the composition cannot achieve flame retardancy and the dimensional stability is not good.
  • CN 107815280A uses bisphenol A epoxy resin, dicyandiamide, magnesium hydroxide, silicon micropowder, etc. to improve the insulation of LED copper clad laminates, but the system does not have high whiteness and high heat discoloration resistance.
  • CN 106381111A uses liquid bisphenol A resin, solid bisphenol A resin, phenolic resin, inorganic fillers, and whitening agents to make the copper clad laminate glue solution achieve high whiteness, good adhesion and UV resistance, but this system is extremely Easy to change color.
  • the purpose of the present invention is to provide a thermosetting epoxy resin composition and a prepreg, laminate and printed circuit board using the thermosetting epoxy resin composition.
  • the thermosetting epoxy resin composition guarantees V0-level flame retardancy, and also has good heat-resistant discoloration and dimensional stability, and can meet the high whiteness, high temperature-resistant whiteness and whiteness of laminates in the LED field. Performance requirements for high dimensional stability.
  • the present invention adopts the following technical solutions:
  • thermosetting epoxy resin composition includes the following components in parts by weight:
  • Component A 2-10 parts of phosphoric anhydride, Component B: 5-40 parts of phosphorus-free acid anhydride, Component C: 5-45 parts of epoxy resin, Component D: 40-70 parts of filler, and group Point E: 0-15 parts of phosphorus-containing flame retardant;
  • the total weight parts of the component A, component B, component C, component D and component E is 100 parts;
  • the phosphoric anhydride has the structure shown in the following formula I or formula II:
  • R 1 and R 2 are each independently selected from any of hydrogen, C1-C5 (for example, C1, C2, C3, C4, C5) alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl
  • C1-C5 for example, C1, C2, C3, C4, C5 alkyl
  • substituted or unsubstituted phenyl substituted or unsubstituted naphthyl
  • R 3 is selected from any one of hydrogen, C1-C5 (e.g. C1, C2, C3, C4, C5) alkyl, siloxy and siloxane group;
  • X 1 and X 2 are each independently selected from Any one of the group, where * represents the position of the group;
  • R 11 and R 12 are each independently selected from any one of C1-C5 alkyl, benzoxazinyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl;
  • the substituent is a halogen atom or a C1-C5 (for example, C1, C2, C3, C4, C5) linear or branched alkyl group;
  • the epoxy resin is selected from one or a combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin and biphenyl epoxy resin.
  • the epoxy resin of the present invention does not contain epoxy resins of other structures than the above-mentioned limited range.
  • epoxy resins other than bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl epoxy resin are used, the dimensional stability and heat discoloration resistance of the composition will be significantly reduced, which cannot meet the requirements of LED The field requires high dimensional stability and high temperature resistance and whiteness of laminates.
  • Organic phosphorus-containing materials have good flame retardancy, but they are usually prone to yellowing at high temperatures.
  • the inventor’s research has found that by using the phosphoric anhydride of the above formula I or formula II in a specific ratio with a specific type of epoxy resin (bisphenol A epoxy resin, bisphenol F epoxy resin and biphenyl ring One or a combination of at least two of the oxy resins) can make the resulting thermosetting epoxy resin composition achieve V0-level flame retardancy, and at the same time have high heat-resistant discoloration and dimensional stability.
  • the weight parts of the phosphoric anhydride is 2-10 parts, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts. Parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts, etc.
  • thermosetting epoxy resin composition when the amount of phosphoric anhydride contained in component A is too small, the resulting thermosetting epoxy resin composition has poor flame retardancy, which is difficult to meet application requirements; when the amount of phosphoric anhydride contained in component A is too large, it will cause The heat discoloration resistance, dimensional stability, and moisture resistance of the thermosetting epoxy resin composition are significantly reduced.
  • the weight of phosphoric anhydride when the weight of phosphoric anhydride is 2-10 parts, the composition can not only meet the V0 flame retardancy, but will not affect the whiteness and heat-resistant discoloration of the thermosetting epoxy resin composition. The performance and dimensional stability bring deteriorating effects.
  • the weight parts of the phosphorus-free acid anhydride is 5-40 parts, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30, 32, 35, 38, 40, etc.
  • thermosetting epoxy resin composition When the amount of phosphorus-free acid anhydride is too small, the heat yellowing resistance of the obtained thermosetting epoxy resin composition will deteriorate; when the amount of phosphorus-free acid anhydride is too much, the peel strength of the resulting thermosetting epoxy resin composition will deteriorate. .
  • the parts by weight of the epoxy resin are 5-45 parts, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts. , 32, 35, 38, 40, 42 or 45, etc.
  • the weight parts of the filler is 40-70 parts, for example, it can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts. Servings or 70 servings etc.
  • the weight parts of the phosphorus-containing flame retardant is 0-15 parts, for example, 0 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 servings, 11 servings, 12 servings, 13 servings, 14 servings, or 15 servings, etc.
  • Phosphorus-containing flame retardants can be selectively added according to the flame retardant effect, but the amount of phosphorus-containing flame retardants cannot exceed 15 parts.
  • the amount of phosphorus-containing flame retardants is excessive, the viscosity of the thermosetting resin composition will be too large, which will easily cause filler dispersion difficulties. Negative effects such as deterioration of peel strength and pits when the composition is composited with reinforcing materials.
  • R 3 in formula I is a siloxy group or a siloxane group.
  • R 3 in formula I is selected from Any one of, wherein n is an integer from 1 to 3 (for example, 1, 2 or 3), and * represents the attachment position of the group.
  • the phosphorus-free acid anhydride is selected from one or a combination of at least two of methyltetrahydrophthalic anhydride, methylnadic anhydride and styrene-maleic anhydride.
  • the styrene-maleic anhydride has the structure shown in the following formula III:
  • n 1 :n 2 0.8-19:1.
  • the number average molecular weight of the styrene-maleic anhydride is 1000-50000, for example, it can be 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10000 , 15000, 20000, 25000, 30000, 35000, 40000, 45000 or 50000, etc.; more preferably 1500-45000, still more preferably 2000-40000.
  • the number average molecular weight in the present invention is the number average molecular weight measured by gel permeation chromatography.
  • the filler is selected from one or a combination of at least two of titanium dioxide, boehmite and aluminum hydroxide.
  • titanium dioxide also known as titanium dioxide
  • the filler is more preferably titanium dioxide.
  • the median particle size of the filler is 0.1-10 ⁇ m; for example, it can be 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, or 10 ⁇ m.
  • thermosetting epoxy resin composition of the present invention in addition to the above-mentioned titanium dioxide, boehmite and aluminum hydroxide, other types of organic or inorganic fillers can be added, such as silica, kaolin, talc, hydrotalcite, silicic acid Calcium, beryllium oxide, boron nitride, glass powder, zinc borate, aluminum nitrogen compounds, silicon nitride, silicon carbide, magnesium oxide, zirconium oxide, mullite, potassium titanate, hollow glass beads, polytetrafluoroethylene powder , Polystyrene powder and other powders, or single crystal fibers of potassium titanate, silicon carbide, silicon nitride or alumina, short glass fibers, etc.
  • organic or inorganic fillers such as silica, kaolin, talc, hydrotalcite, silicic acid Calcium, beryllium oxide, boron nitride, glass powder, zinc borate, aluminum nitrogen compounds, silicon nitride, silicon carbide,
  • the addition amount is preferably 10-60% of the total weight of the thermosetting epoxy resin composition, more preferably 10-40%; if the amount exceeds 60%, the viscosity of the resin system will increase, and the cured laminate of the composition will Makes PCB processing difficult.
  • the phosphorus-containing flame retardant is aluminum phosphate and/or a high melting point phosphorus-containing flame retardant, and the melting point of the high melting point phosphorus-containing flame retardant is above 260°C.
  • These two types of phosphorus-containing flame retardants provide flame retardant properties and also have good heat resistance and discoloration properties, so they are suitable for the present invention.
  • the high melting point phosphorus-containing flame retardant has a structure represented by the following formula (1) or formula (2):
  • Y is a direct bond, an aryl group, an alkyl group, a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted cycloalkenyl group.
  • the substituents are C1-C6 (E.g. C1, C2, C3, C4, C5, C6) alkyl;
  • R 6 , R 7 , R 8 , and R 9 are each independently hydrogen, C1-C6 (e.g. C1, C2, C3, C4, C5, C6) alkyl, C6-C12 (e.g. C6, C7, C8, C10, C12) aryl or C7-C15 (e.g. C7, C8, C9, C10, C12, C13, C15) aralkyl; or R 6 , R 7 , R 8 , and R 9 together form a saturated or unsaturated ring, The saturated or unsaturated ring is optionally substituted with C1-C6 alkyl;
  • C1-C6 e.g. C1, C2, C3, C4, C5, C6
  • C6-C12 e.g. C6, C7, C8, C10, C12
  • C7-C15 e.g. C7, C8, C9, C10, C12, C13, C15
  • n 1 , m 2 , m 3 , and m 4 are each independently 1, 2, 3, or 4;
  • R 4, R '4, R 5, R' 5 are each independently hydrogen or C1-C6 alkyl group
  • a and b are each independently 0, 1, 2, 3, 4, or 5, and Y is an aryl group or a direct bond, a and b are not 0.
  • the structural formula of the high melting point phosphorus-containing flame retardant is as follows:
  • thermosetting epoxy resin composition further includes a catalyst.
  • the weight part of the catalyst is 0.001-5 parts, for example, Yes 0.001 part, 0.002 part, 0.005 part, 0.008 part, 0.01 part, 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 2 part, 3 part, 4 part or 5 Parts, etc.; more preferably 0.02-4 parts, still more preferably 0.05-3 parts.
  • the amount of catalyst used depends on the type of epoxy resin, the type of curing agent and the type of catalyst.
  • the amount of the catalyst used in the present invention is 0.001-5.0 wt% relative to the total amount of the thermosetting epoxy resin composition. If the amount of catalyst is too much (more than 5.0wt%), the reactivity of the thermosetting epoxy resin composition will be too high, and it is easy to produce by-products, which will have an adverse effect on the uniformity of the curing reaction conversion rate; if the amount of the catalyst is too high If it is low, the reactivity of the resin composition is too low, which is not conducive to the production of the prepreg.
  • An empirical principle for using the catalyst in the present invention is that the gelation time of the glue prepared by the resin composition should not be less than 120s.
  • the catalyst is selected from one or a combination of at least two of tertiary amines, tertiary phosphines, quaternary ammonium salts, quaternary phosphonium salts, organometallic complexes and imidazole compounds.
  • tertiary amines include: triethylamine, tributylamine, dimethylamine ethanol, N,N-dimethyl-aminomethylphenol, benzyldimethylamine, etc.;
  • tertiary phosphines examples include: triphenylphosphine, etc.;
  • quaternary ammonium salts are: tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, cetyl Trimethylammonium bromide, etc.;
  • quaternary phosphonium salts include: tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetrabutyl phosphonium iodide, tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium iodide, Ethyl triphenyl phosphonium chloride, propyl triphenyl phosphonium chloride, propyl triphenyl phosphonium bromide, propyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, butyl triphenyl Phosphonium bromide, butyl triphenyl phosphonium iodide, etc.;
  • organometallic complexes are: zinc acetate, copper acetate, nickel acetate, zinc octoate, copper octoate, iron octoate, cobalt octoate, acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, iron acetylacetonate, zinc naphthenate, Cobalt acetylacetonate, copper naphthenate, iron naphthenate, cobalt naphthenate, etc.;
  • imidazole compounds are: 2-methylimidazole, 2-ethyl-4methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-decylimidazole Heptaalkylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, etc.
  • the above-mentioned catalysts can be used singly or in combination of multiple types.
  • the present invention provides a resin adhesive film, which is formed by semi-curing the thermosetting epoxy resin composition described in the first aspect after baking and heating.
  • the present invention provides a resin-coated copper foil.
  • the resin-coated copper foil is prepared by coating the thermosetting epoxy resin composition of the first aspect on the copper foil and forming a semi-cured state by heating. get.
  • the present invention provides a prepreg, the prepreg comprising a reinforcing material, and the thermosetting epoxy resin composition of the first aspect attached to the reinforcing material after being impregnated and dried.
  • thermosetting epoxy resin composition described in the first aspect can be dissolved or dispersed in a solvent to obtain a resin glue solution; then the reinforcing material can be infiltrated with the resin glue solution, Heat and dry to make the thermosetting epoxy resin composition in a semi-cured state to obtain a semi-cured sheet.
  • examples of usable solvents include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, and primary alcohol; Ethers such as methyl ether and propylene glycol monomethyl ether; esters such as propylene glycol methyl ether acetate and ethyl acetate; aprotic solvents such as N,N-dimethylformamide and N,N-diethylformamide.
  • the above-mentioned solvents can be used singly or in a mixture of multiple types.
  • the reinforcing material can be an inorganic or organic reinforcing material.
  • inorganic reinforcing materials include woven fabrics, non-woven fabrics, or paper such as glass fiber, carbon fiber, boron fiber, and metal.
  • the glass fiber cloth or non-woven cloth can be E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, high silica cloth, etc.
  • organic reinforcing materials include woven fabrics or non-woven fabrics or paper made of polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, and syndiotactic polystyrene.
  • the temperature for heating and drying can be 80-250°C, for example, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or 250°C, etc.; time can be 1-30min, for example, it can be 1min, 2min, 3min, 5min, 8min, 10min, 12min, 15min, 18min, 20min, 22min , 25min, 28min or 30min, etc.
  • thermosetting epoxy resin composition in the prepreg can be 30-80wt%; for example, it can be 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt% Or 80wt% etc.
  • the present invention provides a laminated board comprising one or at least two laminated prepregs of the fourth aspect.
  • the present invention provides a metal-clad laminate, the metal-clad laminate includes one or at least two stacked prepregs of the fourth aspect, and a prepreg covered or laminated Metal foil on one or both sides of the prepreg.
  • the present invention does not have special restrictions on the preparation method of the metal-clad laminate.
  • the following methods can be used:
  • metal foil copper, brass, aluminum, nickel, and alloys or composite metal foils of these metals can be used.
  • the pressing conditions of the laminate should be selected according to the actual situation of the epoxy resin composition. If the pressing pressure is too low, there will be voids in the laminate, and its electrical properties will decrease; if the lamination pressure is too high, there will be too much internal stress in the laminate, which will reduce the dimensional stability of the laminate. To meet the molding pressure to press the board to meet the required requirements.
  • the general guidelines for conventional pressed laminates are: the lamination temperature is 130-250°C, the pressure is 3-50 kgf/cm 2 , and the hot pressing time is 60-240 minutes.
  • the above-mentioned prepregs and metal-clad laminates can be used to make printed circuit boards or complex multilayer circuit boards by addition or subtraction.
  • the present invention provides a printed circuit board, which is manufactured by removing part of the metal foil on the surface of the metal-clad laminate as described in the sixth aspect to form a circuit.
  • thermosetting epoxy resin composition provided by the present invention can be used in addition to the production of resin sheets, resin composite metal copper foils, prepregs, laminates, copper clad laminates, and printed circuit boards. It is used to make adhesives, coatings, composite materials, and can also be used in the construction, aviation, shipbuilding, and automotive industries.
  • the present invention has the following beneficial effects:
  • the present invention uses phosphoric anhydride with the structure of Formula I or Formula II to match a specific type of epoxy resin in a specific ratio, so that the resulting thermosetting epoxy resin composition achieves V0 flame retardancy while having relatively high flame retardancy. High heat yellowing resistance, dimensional stability and humidity resistance, especially suitable for LED and other fields.
  • Examples 1-7 each provide a copper clad laminate, and the preparation method is as follows:
  • Component A contains phosphoric anhydride
  • component B does not contain phosphorus acid anhydride
  • component C epoxy resin, component D filler, and component E phosphorus-containing flame retardant, catalyst, etc. are added to the solvent in proportion, and mixed uniformly, Obtain resin glue;
  • the obtained prepregs were laminated according to a certain number, and a copper foil of 18 microns was added on each side, and cured in a press at 200° C. for 90 minutes to obtain a copper-clad laminate.
  • Examples 8-18 each provide a copper-clad laminate, which is different from Example 1 only in the types and amounts of raw materials used.
  • the types of raw materials used in Examples 8-18, the amount (parts by weight) and the performance data of the obtained copper clad laminate are shown in Table 3 and Table 4:
  • a copper clad laminate is provided.
  • the difference from Example 1 is that the component A containing phosphoric anhydride 1 is replaced with an equivalent amount of non-reactive flame retardant aluminum phosphate.
  • a copper-clad laminate is provided.
  • the difference from Example 2 is that the addition amount of component A containing phosphoric anhydride 2 is 15 parts by weight.
  • a copper-clad laminate is provided.
  • the difference from Example 1 is that the component A containing phosphoric anhydride 1 is replaced with an equivalent amount of flame-retardant curing agent phosphorus-containing phenolic.
  • Example 1 A copper clad laminate is provided. The difference from Example 1 is that the component A contains phosphoric anhydride 1 is replaced with a flame retardant curing agent phosphorus-containing phenolic, and the phosphorus content in the resin composition is kept the same as that of Example 1.
  • Example 3 Each provides a copper clad laminate.
  • the difference from Example 3 is that the type of component C epoxy resin is different.
  • ⁇ means a small amount of discoloration
  • the water absorption rate is the test weight change rate after making a 100mm ⁇ 100mm laminate board in a pressure cooker at 103kPa and 121°C for 2 hours.
  • the copper clad laminate prepared by using the thermosetting epoxy resin composition provided by the present invention has excellent dimensional stability, flame retardancy and heat discoloration resistance, and low The water absorption rate. Its flame retardant grade reaches V0 grade, IPC-TM650-2.4.39 test dimensional change rate is 180-290ppm, color has no obvious change after high temperature treatment at 200°C, and water absorption rate is 0.17-0.31%.
  • Comparative Example 1 uses the same amount of aluminum phosphate salt flame retardant instead of phosphoric anhydride 1, and the resulting copper clad laminate has poorer dimensional stability. Can not reach V0 flame retardant.
  • Example 2 Compared with Example 2, in Comparative Example 2, because component A contains too much phosphoric anhydride, the dimensional stability, heat discoloration resistance, and water absorption performance of the obtained copper-clad laminate are significantly deteriorated.
  • Comparative Example 3 uses the same amount of flame-retardant curing agent phosphorus-containing phenolic instead of phosphoric anhydride 1.
  • the obtained copper clad laminate can not achieve V0 flame retardancy, and the heat-resistant discoloration property is also significantly changed. difference.
  • Comparative Example 4 uses the flame-retardant curing agent phosphorus-containing phenolic instead of phosphoric anhydride 1, and keeps the phosphorus content in the resin composition unchanged. Although the obtained copper clad laminate reaches the V0 flame retardant level, However, the heat discoloration resistance and dimensional stability are significantly worsened.
  • Comparative Example 5 did not use the type of epoxy resin defined in the present invention, and Comparative Examples 6-7 were added with other types of epoxy resins, so the resulting copper clad laminates had heat-resistant discoloration Sex is significantly worse.

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Abstract

提供一种热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板。该热固性环氧树脂组合物包括如下重量份数的组分：含磷酸酐2-10份，不含磷的酸酐5-40份，环氧树脂5-45份，填料40-70份，以及含磷阻燃剂0-15份；上述各组分的总重量份数为100份；所述含磷酸酐具有式I或式II所示结构；所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂和联苯环氧树脂中的一种或至少两种的组合。该热固性环氧树脂组合物固化后在保证V0级阻燃性的同时，还具有良好的耐热变色性和尺寸稳定性，可用于LED领域印制线路板基材的制备。

Description

[根据细则37.2由ISA制定的发明名称]　热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板 技术领域
本发明属于印制线路板技术领域，具体涉及一种热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板。
背景技术
近年来，以LED为代表的光半导体被用于显示用途、可动装置、手机灯背光光源、传感器、车载部件等方面。随着LED功率、亮度的提高，要求用于LED安装用印制线路板中的层压板/覆金属箔层压板具有优异的耐光性，尤其是在高温后具有较高的白度。此外随着人们对环境日益重视以及无铅回流焊工艺的推广，为了安装的稳定性，对层压板/覆金属箔层压板的阻燃性能、尺寸稳定性也提出日益严苛的要求。
CN 109181604A使用双酚A/双酚F环氧树脂、甲基四氢邻苯二酐或纳迪克酸酐、催化剂获得高透明环氧树脂胶，但是该组合并不阻燃而且也不用于预浸料及层压板。
CN 108641650A披露使用双酚F环氧、端羧基丁基橡胶、二胺基二苯砜、咪唑、表面活性剂、氧化铝、氮化硼、乙二醇甲醚用于LED线路环氧树脂胶，但是该体系不具有高白度，高温处理后耐热变色性差。
CN 103459493A使用双酚A骨架环氧树脂、脂环族环氧树脂、芳香族多羧酸的完全氢化物或部分氢化物的酸酐、二氧化钛和分散剂制备树脂组合物，达到具有高剥离强度和热处理后高反射率的目的，但是该组合物无法实现阻燃并且尺寸稳定性也不好。
CN 107815280A使用双酚A环氧树脂、双氰胺、氢氧化镁、硅微粉等改善LED覆铜板绝缘性，但是该体系不具有高白度和高耐热变色性。
CN 106381111A使用液态双酚A树脂、固态双酚A树脂、酚醛树脂、无机填料、增白剂来使覆铜板胶液达到高白度、良好附着力和抗紫外线功能，但是该体系在高温后极易变色。
因此，在本领域期望得到一种兼具高白度、高耐热变色性、高尺寸稳定性和高阻燃性的层压板/覆金属箔层压板，因满足LED等领域对印制线路板基材的性能要求。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板。该热固性环氧树脂组合物固化后在保证V0级阻燃性的同时，还具有良好的耐热变色性和尺寸稳定性，能够满足LED领域对层压板的高白度、高耐温白度和高尺寸稳定性的性能要求。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种热固性环氧树脂组合物，所述热固性环氧树脂组合物包括如下重量份数的组分：
组分A：含磷酸酐2-10份，组分B：不含磷的酸酐5-40份，组分C：环氧树脂5-45份，组分D：填料40-70份，以及组分E：含磷阻燃剂0-15份；
所述组分A、组分B、组分C、组分D和组分E的总重量份数为100份；
所述含磷酸酐具有如下式I或式II所示结构：
Figure PCTCN2020082466-appb-000001
其中，R 1和R 2各自独立地选自氢、C1-C5(例如C1、C2、C3、C4、C5)烷基、取代或未取代的苯基、取代或未取代的萘基中的任意一种；
R 3选自氢、C1-C5(例如C1、C2、C3、C4、C5)烷基、硅氧基和硅氧烷基中的任意一种；
X 1和X 2各自独立地选自
Figure PCTCN2020082466-appb-000002
Figure PCTCN2020082466-appb-000003
中的任意一种，其中*代表基团的连接位置；
R 11和R 12各自独立地选自C1-C5烷基、苯并噁嗪基、取代或未取代的苯基、取代或未取代的萘基中的任意一种；
如上所述基团含有取代基时，所述取代基为卤素原子或C1-C5(例如C1、C2、C3、C4、C5)的直链或支链烷基；
所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂和联苯环氧树脂中的一种或至少两种的组合。
需要说明的是，本发明的环氧树脂不含有除上述限定范围之外的其它结构的环氧树脂。当采用除双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂以外的环氧树脂时，会导致组合物的尺寸稳定性和耐热变色性明显下降，无法满足LED领域对层压板的高尺寸稳定性和高耐温白度的性能要求。
有机含磷材料具有良好的阻燃性，但其在高温下通常容易发生黄变。发明人研究发现，通过采用上述式I或式II结构的含磷酸酐在特定的比例下搭配特定种类的环氧树脂(双酚A型环氧树脂、双酚F型环氧树脂和联苯环氧树脂中 的一种或至少两种的组合)，能够使得到的热固性环氧树脂组合物在达到V0级阻燃性的同时，具有较高的耐热变色性和尺寸稳定性。
本发明中，所述含磷酸酐的重量份数为2-10份，例如可以是2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份、6.5份、7份、7.5份、8份、8.5份、9份、9.5份或10份等。
本发明中，当组分A含磷酸酐的用量过少时，得到的热固性环氧树脂组合物的阻燃性较差，难以满足应用需要；当组分A含磷酸酐的用量过多时，会导致热固性环氧树脂组合物的耐热变色性、尺寸稳定性和耐湿性均明显下降。而在本发明中，当含磷酸酐的重量份数为2-10份时，既能使组合物满足V0级阻燃性，也不会对热固性环氧树脂组合物的白度、耐热变色性和尺寸稳定性带来劣化影响。
所述不含磷的酸酐的重量份数为5-40份，例如可以是5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份、38份或40份等。
不含磷的酸酐用量过少时，得到的热固性环氧树脂组合物的耐热黄变性会变差；当不含磷的酸酐用量过多是得到的热固性环氧树脂组合物的剥离强度会出现劣化。
所述环氧树脂的重量份数为5-45份，例如可以是5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份、38份、40份、42份或45份等。
当环氧树脂过多或过少时都会带来尺寸稳定性变差的风险。
所述填料的重量份数为40-70份，例如可以是40份、42份、45份、48份、50份、52份、55份、58份、60份、62份、65份、68份或70份等。
所述含磷阻燃剂的重量份数为0-15份，例如可以是0份、1份、2份、3份、4份、5份、6份、7份、8份、9份、10份、11份、12份、13份、14份或15份等。
根据阻燃效果可以选择性添加含磷阻燃剂，但是含磷阻燃剂用量不能超过15份，当含磷阻燃剂过量时会造成热固性树脂组合物的粘度过大容易引起填料分散困难、剥离强度劣化、组合物复合增强材料时出现凹点等负面效果。
作为本发明的优选技术方案，式I中R 3为硅氧基或硅氧烷基。
优选地，式I中R 3选自
Figure PCTCN2020082466-appb-000004
Figure PCTCN2020082466-appb-000005
中的任意一种，其中n为1-3(例如1、2或3)的整数，*代表基团的连接位置。
作为本发明的优选技术方案，所述不含磷的酸酐选自甲基四氢邻苯二甲酸酐、甲基纳迪克酸酐和苯乙烯-马来酸酐中的一种或至少两种的组合。
优选地，所述苯乙烯-马来酸酐具有如下式III所示结构：
Figure PCTCN2020082466-appb-000006
其中，n 1:n 2＝0.8-19:1。
优选地，所述苯乙烯-马来酸酐的数均分子量为1000-50000，例如可以是1000、1500、2000、2500、3000、3500、4000、4500、5000、6000、7000、8000、9000、10000、15000、20000、25000、30000、35000、40000、45000或50000 等；更优选为1500-45000，进一步优选为2000-40000。
需要说明的是，本发明中所述数均分子量均是通过凝胶渗透色谱法测得的数均分子量。
作为本发明的优选技术方案，所述填料选自二氧化钛、勃姆石和氢氧化铝中的一种或至少两种的组合。其中，二氧化钛又称钛白粉，是一种白色填料，有助于提高热固性环氧树脂组合物和使用其的层压板的白度。因此，所述填料更优选为二氧化钛。
优选地，所述填料的中位粒径为0.1-10μm；例如可以是0.1μm、0.5μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm或10μm等。
本发明热固性环氧树脂组合物中，除了上述二氧化钛、勃姆石和氢氧化铝外，还可以添加其他种类的有机或无机填料，例如可以是二氧化硅、高岭土、滑石粉、水滑石、硅酸钙、氧化铍、氮化硼、玻璃粉、硼酸锌、铝氮化合物、氮化硅、碳化硅、氧化镁、氧化锆、莫来石、钛酸钾、中空玻璃微珠、聚四氟乙烯粉末、聚苯乙烯粉末等的粉体，或者钛酸钾、碳化硅、氮化硅或氧化铝的单晶纤维、玻璃短纤维等。其添加量优选为热固性环氧树脂组合物总重量的10-60％，更优选为10-40％；若其用量超过60％，树脂体系的粘度会增高，同时组合物固化后的层压板会使得PCB加工困难。
作为本发明的优选技术方案，所述含磷阻燃剂为磷酸铝盐和/或高熔点含磷阻燃剂，所述高熔点含磷阻燃剂的熔点在260℃以上。这两类含磷阻燃剂在提供阻燃性能的同时还具有耐热变色性好的特点，因此适用于本发明。
优选地，所述高熔点含磷阻燃剂具有如下式(1)或式(2)所示结构：
Figure PCTCN2020082466-appb-000007
其中，Y为直连键、芳基、烷基、取代或未取代的环烷基或取代或未取代的环烯基，如上所述基团含有取代基时，所述取代基为C1-C6(例如C1、C2、C3、C4、C5、C6)烷基；
R 6、R 7、R 8、R 9各自独立地为氢、C1-C6(例如C1、C2、C3、C4、C5、C6)烷基、C6-C12(例如C6、C7、C8、C10、C12)芳基或C7-C15(例如C7、C8、C9、C10、C12、C13、C15)芳烷基；或者R 6、R 7、R 8、R 9合起来形成饱和或不饱和的环，所述饱和或不饱和的环任选经C1-C6烷基取代；
m 1、m 2、m 3、m 4各自独立地为1、2、3或者4；
R 4、R' 4、R 5、R' 5各自独立地为氢或C1-C6烷基；
a、b各自独立地为0、1、2、3、4或5，且Y为芳基或直连键时，a、b不为0。
作为实际案例的高熔点含磷阻燃剂的结构式如下：
Figure PCTCN2020082466-appb-000008
本发明中优选采用上述种类的含磷阻燃剂。而10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-膦菲-10-氧化物、10-(2,5-二羟基萘基)-10-氢-9-氧杂-10-膦菲-10-氧化物、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或含磷酚醛等由于高温下白度衰减过快、耐热变色性差不适用于本发明。
作为本发明的优选技术方案，热固性环氧树脂组合物还包括催化剂。
优选地，以所述组分A、组分B、组分C、组分D和组分E的总重量份数为100份计，所述催化剂的重量份数为0.001-5份，例如可以是0.001份、0.002份、0.005份、0.008份、0.01份、0.03份、0.05份、0.08份、0.1份、0.3份、0.5份、0.8份、1份、2份、3份、4份或5份等；更优选为0.02-4份，进一步优选为0.05-3份。
催化剂的使用量视环氧树脂种类、固化剂的种类和催化剂种类而定。本发明中催化剂的用量相对于热固性环氧树脂组合物的总量为0.001～5.0wt％。若催化剂的用量过多(超过5.0wt％)，将会导致热固性环氧树脂组合物的反应性过高，容易产生副产物，对固化反应转化率的均匀性产生不良影响；若催化剂的 用量过低，会导致树脂组合物的反应性过低，不利于半固化片的制作。本发明中使用催化剂的一个经验性原则为，树脂组合物配制的胶水的凝胶化时间不应低于120s。
优选地，所述催化剂选自三级胺、三级膦、季铵盐、季鏻盐、有机金属络合物和咪唑化合物中的一种或至少两种的组合。
其中，三级胺的实例有：三乙基胺、三丁基胺、二甲基胺乙醇、N,N-二甲基-胺基甲基酚、苯甲基二甲基胺等；
三级膦的实例有：三苯基膦等；
季铵盐的实例有：四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、苄基三甲基氯化铵、苄基三乙基氯化铵、十六烷基三甲基溴化铵等；
季鏻盐的具体实例有：四丁基氯化鏻、四丁基溴化鏻、四丁基碘化鏻、四苯基氯化鏻、四苯基溴化鏻、四苯基碘化鏻、乙基三苯基氯化鏻、丙基三苯基氯化鏻、丙基三苯基溴化鏻、丙基三苯基碘化鏻、丁基三苯基氯化鏻、丁基三苯基溴化鏻、丁基三苯基碘化鏻等；
有机金属络合物实例有：醋酸锌、醋酸铜、醋酸镍、辛酸锌、辛酸铜、辛酸铁、辛酸钴、乙酰丙酮酮、乙酰丙酮锌、乙酰丙酮镍、乙酰丙酮铁、环烷酸锌、乙酰丙酮钴、环烷酸铜、环烷酸铁、环烷酸钴等；
咪唑类化合物实例有：2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、2-异丙基咪唑、2-苯基-4-甲基咪唑、2-十二烷基咪唑、1-氰乙基-2-甲基咪唑等。
上述催化剂可以单独使用，也可以多种混合使用。
第二方面，本发明提供一种树脂胶膜，所述树脂膜由第一方面所述的热固性环氧树脂组合物经烘烤加热后半固化而成。
第三方面，本发明提供一种涂树脂铜箔，所述涂树脂铜箔是通过将第一方面所述的热固性环氧树脂组合物涂覆于铜箔上，并经由加热形成半固化态而得到。
第四方面，本发明提供一种半固化片，所述半固化包括增强材料，和通过含浸干燥后附着在所述增强材料上的第一方面所述的热固性环氧树脂组合物。
本发明对半固化片的制备方法没有特殊限制，示例性的，可以将第一方面所述的热固性环氧树脂组合物溶解或分散在溶剂中，得到树脂胶液；然后用树脂胶液浸润增强材料，加热干燥，使热固性环氧树脂组合物处于半固化状态，得到半固化片。
其中，可使用的溶剂的例子有：丙酮、甲基乙基酮、甲基异丁基酮等酮类；甲苯、二甲苯等烃类；甲醇、乙醇、伯醇等醇类；乙二醇单甲醚、丙二醇单甲醚等醚类；丙二醇甲醚醋酸酯、乙酸乙酯等酯类；N,N-二甲基甲酰胺、N,N-二乙基甲酰胺等非质子溶剂。上述溶剂可以单独使用，也可以多种混合使用。
增强材料可为无机或有机增强材料。无机增强材料可列举的有：玻璃纤维、碳纤维、硼纤维、金属等的机织织物或无纺布或纸。其中，玻璃纤维布或无纺布可以使E-glass、Q型布、NE布、D型布、S型布、高硅氧布等。有机增强材料可列举的有：聚酯、聚胺、聚丙烯酸、聚酰亚胺、芳纶、聚四氟乙烯、间规聚苯乙烯等制造的织布或无纺布或纸。
加热干燥的温度可以为80-250℃，例如可以是80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃或250℃等；时间可以为1-30min，例如可以是1min、2min、3min、5min、8min、10min、12min、15min、18min、20min、22min、25min、28min或30min等。
半固化片中的热固性环氧树脂组合物的含量可以为30-80wt％；例如可以是30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％或80wt％等。
第五方面，本发明提供一种层压板，所述层压板包括一张或至少两张叠合的第四方面所述的半固化片。
第六方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板包括一张或至少两张叠合的第四方面所述的半固化片，以及覆于一张半固化片或叠合后的半固化片的一侧或两侧的金属箔。
本发明对覆金属箔层压板的制备方法没有特殊限制，示例性的，可以采用如下方法：
将一个或多个半固化片裁剪成一定尺寸进行叠片后送入层压设备中进行层压，同时将金属箔放置在半固化片的一侧或两侧，通过热压成型将半固化压制形成覆金属箔层压板。
其中，金属箔可以使用铜、黄铜、铝、镍、以及这些金属的合金或复合金属箔。
层压板的压制条件应根据环氧树脂组合物的实际情况选择。如果压制压力过低，会使层压板中存在空隙，其电性能会下降；层压压力过大会使层压板中存在过多的内应力，使得层压板的尺寸稳定性能下降，这些都需要通过合适的满足模塑的压力来压制板材来达到所需的要求。对于常规的压制层压板的通常指导原则为：层压温度为130～250℃，压力为3-50kgf/cm 2，热压时间为60-240分钟。可以使用上述半固化片、覆金属箔层压板通过加成或减层法制作印制线路板或复杂的多层电路板。
第七方面，本发明提供一种印制线路板，所述印制线路板是通过去除第六 方面所述的覆金属箔层压板表面的部分金属箔而形成电路的方法制得。
需要说明的是，本发明提供的热固性环氧树脂组合物除了可以用于制作树脂片、树脂复合物金属铜箔、半固化片、层压板、覆铜箔层压板、印制线路板之外，还可用于用来制作胶黏剂、涂料、复合材料，也可用于建筑、航空、船舶、汽车工业。
与现有技术相比，本发明具有以下有益效果：
本发明通过采用具有式I或式II结构的含磷酸酐在特定的比例下搭配特定种类的环氧树脂，从而使得到的热固性环氧树脂组合物在达到V0级阻燃性的同时，具有较高的耐热黄变性、尺寸稳定性和耐湿性，特别适用于LED等领域。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
合成例1：合成含磷酸酐1
纳迪克酸酐
Figure PCTCN2020082466-appb-000009
和磷化合物
Figure PCTCN2020082466-appb-000010
在引发剂过氧化苯甲酰的存在下发生反应，其反应温度为135℃，将纳迪克酸酐中的碳碳双键与磷化合物中的活泼氢基反应，获得含磷酸酐1。
含磷酸酐1：
Figure PCTCN2020082466-appb-000011
合成例2：合成含磷酸酐2
内甲基纳迪克酸酐
Figure PCTCN2020082466-appb-000012
和磷化合物
Figure PCTCN2020082466-appb-000013
在引发剂过氧化苯甲酰的存在下发生反应，其反应温度为135℃，将纳迪克酸酐中的碳碳双键与磷化合物中的活泼氢基反应，获得含磷酸酐2。
含磷酸酐2：
Figure PCTCN2020082466-appb-000014
合成例3：合成含磷酸酐3
将纳迪克酸酐
Figure PCTCN2020082466-appb-000015
和磷化合物
Figure PCTCN2020082466-appb-000016
在引发剂过氧化苯甲酰的存在下发生反应，其反应温度为135℃，将纳迪克酸酐中的碳碳双键与磷化合物中的活泼氢基反应，获得含磷酸酐3。
含磷酸酐3：
Figure PCTCN2020082466-appb-000017
合成例4：合成含磷酸酐4
将含硅氧基纳迪克酸酐
Figure PCTCN2020082466-appb-000018
和磷化合物
Figure PCTCN2020082466-appb-000019
在引 发剂过氧化苯甲酰的存在下发生反应，其反应温度为135℃，将纳迪克酸酐中的碳碳双键与磷化合物中的活泼氢基反应，获得含磷酸酐4。
含磷酸酐4：
Figure PCTCN2020082466-appb-000020
本发明实施例和对比例中使用的原料来源如下表1所示：
表1
Figure PCTCN2020082466-appb-000021
Figure PCTCN2020082466-appb-000022
实施例1-7
实施例1-7各提供一种覆铜箔层压板，其制备方法如下：
(1)树脂胶液的制备
将组分A含磷酸酐、组分B不含磷的酸酐、组分C环氧树脂、组分D填料，以及组分E含磷阻燃剂、催化剂等按比例加入溶剂中，混合均匀，得到树脂胶液；
(2)半固化片的制备
将树脂胶液浸渍在玻璃布上后，在155℃烘箱中烘烤去除溶剂，得到半固化片；
(3)覆铜箔层压板的制备
将得到的半固化片按照一定的数量叠合，两面各加一张18微米铜箔，在压机中200℃固化90分钟，得到覆铜箔层压板。
实施例1-7中采用的原料种类、用量(重量份)和得到的覆铜箔层压板的性能数据如下表2所示：
表2
Figure PCTCN2020082466-appb-000023
Figure PCTCN2020082466-appb-000024
实施例8-18
实施例8-18各提供一种覆铜箔层压板，与实施例1的区别仅在于使用的原料种类和用量不同。实施例8-18采用的原料种类、用量(重量份)和得到的覆铜箔层压板的性能数据如下表3和表4所示：
表3
Figure PCTCN2020082466-appb-000025
Figure PCTCN2020082466-appb-000026
表4
Figure PCTCN2020082466-appb-000027
Figure PCTCN2020082466-appb-000028
对比例1
提供一种覆铜箔层压板，与实施例1的区别在于，将组分A含磷酸酐1替换为等量的非反应型阻燃剂磷酸铝盐。
对比例2
提供一种覆铜箔层压板，与实施例2的区别在于，组分A含磷酸酐2的添加量为15重量份。
对比例3
提供一种覆铜箔层压板，与实施例1的区别在于，将组分A含磷酸酐1替换为等量的阻燃固化剂含磷酚醛。
对比例4
提供一种覆铜箔层压板，与实施例1的区别在于，将组分A含磷酸酐1替换为阻燃固化剂含磷酚醛，且保持树脂组合物中磷含量与实施例1相同。
对比例5-7
各提供一种覆铜箔层压板，与实施例3的区别在于，组分C环氧树脂的种类不同。
对比例1-7采用的原料种类、用量(重量份)和得到的覆铜箔层压板的性能数据如下表5所示：
表5
Figure PCTCN2020082466-appb-000029
Figure PCTCN2020082466-appb-000030
上述性能的测试方法如下：
1、尺寸稳定性：300mm×300mm的层压板尺寸在影像观测上测试尺寸变化率，方法参照IPC-TM650-2.4.39。
2、耐热变色性：
制作成50mm×50mm的层压板在200℃高温下处理4小时后确认其有无变色。
○表示几乎没有变色；
△表示少量变色；
×表示黄变。
3、阻燃性：按照UL94所规定的燃烧性方法进行测定。
4、吸水率：制作成100mm×100mm的层压板在高压锅103kPa，121℃条件下处理2小时后测试重量变化率即为吸水率。
由上述表2-表4的测试结果可以看出，采用本发明提供的热固性环氧树脂组合物制备的覆铜箔层压板具有优良的尺寸稳定性、阻燃性和耐热变色性，以及低的吸水率。其阻燃等级达到V0级，IPC-TM650-2.4.39测试尺寸变化率为180-290ppm，200℃高温处理后颜色无明显变化，吸水率为0.17-0.31％。
由表5的测试结果可以看出，相较于实施例1，对比例1采用等量的磷酸铝盐阻燃剂代替含磷酸酐1，得到的覆铜箔层压板尺寸稳定性变差，也无法达到 V0级阻燃。
相较于实施例2，对比例2由于组分A含磷酸酐的添加量过多，因此得到的覆铜箔层压板的尺寸稳定性、耐热变色性、吸水率性能都明显变差。
相较于实施例1，对比例3采用等量的阻燃固化剂含磷酚醛代替含磷酸酐1，得到的覆铜箔层压板既不能达到V0级阻燃，而且耐热变色性也明显变差。
相较于实施例1，对比例4采用阻燃固化剂含磷酚醛代替含磷酸酐1，并保持树脂组合物中磷含量不变，得到的覆铜箔层压板虽然达到了V0级阻燃，但耐热变色性和尺寸稳定性明显变差。
相较于实施例3，对比例5由于未采用本发明所限定种类的环氧树脂，对比例6-7由于添加有其他种类的环氧树脂，因此得到的覆铜箔层压板的耐热变色性明显变差。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种热固性环氧树脂组合物，其特征在于，所述热固性环氧树脂组合物包括如下重量份数的组分：
    组分A：含磷酸酐2-10份，组分B：不含磷的酸酐5-40份，组分C：环氧树脂5-45份，组分D：填料40-70份，以及组分E：含磷阻燃剂0-15份；
    所述组分A、组分B、组分C、组分D和组分E的总重量份数为100份；
    所述含磷酸酐具有如下式I或式II所示结构：
    Figure PCTCN2020082466-appb-100001
    其中，R 1和R 2各自独立地选自氢、C1-C5烷基、取代或未取代的苯基、取代或未取代的萘基中的任意一种；
    R 3选自氢、C1-C5烷基、硅氧基和硅氧烷基中的任意一种；
    X 1和X 2各自独立地选自
    Figure PCTCN2020082466-appb-100002
    Figure PCTCN2020082466-appb-100003
    中的任意一种，其中*代表基团的连接位置；
    R 11和R 12各自独立地选自C1-C5烷基、苯并噁嗪基、取代或未取代的苯基、取代或未取代的萘基中的任意一种；
    如上所述基团含有取代基时，所述取代基为卤素原子或C1-C5的直链或支链烷基；
    所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂和联苯环氧树脂中的一种或至少两种的组合。
  2. 根据权利要求1所述的热固性环氧树脂组合物，其特征在于，式I中R 3为硅氧基或硅氧烷基；
    优选地，式I中R 3选自
    Figure PCTCN2020082466-appb-100004
    Figure PCTCN2020082466-appb-100005
    中的任意一种，其中n为1-3的整数，*代表基团的连接位置；
    优选地，所述不含磷的酸酐选自甲基四氢邻苯二甲酸酐、甲基纳迪克酸酐和苯乙烯-马来酸酐中的一种或至少两种的组合；
    优选地，所述苯乙烯-马来酸酐具有如下式III所示结构：
    Figure PCTCN2020082466-appb-100006
    其中，n 1:n 2＝0.8-19:1；
    优选地，所述苯乙烯-马来酸酐的数均分子量为1000-50000，更优选为1500-45000，进一步优选为2000-40000；
    优选地，所述填料选自二氧化钛、勃姆石和氢氧化铝中的一种或至少两种的组合，优选为二氧化钛；
    优选地，所述填料的中位粒径为0.1-10μm。
  3. 根据权利要求1或2所述的热固性环氧树脂组合物，其特征在于，所述含磷阻燃剂为磷酸铝盐和/或高熔点含磷阻燃剂，所述高熔点含磷阻燃剂的熔点 在260℃以上；
    优选地，所述高熔点含磷阻燃剂具有如下式(1)或式(2)所示结构：
    Figure PCTCN2020082466-appb-100007
    其中，Y为直连键、芳基、烷基、取代或未取代的环烷基或取代或未取代的环烯基，如上所述基团含有取代基时，所述取代基为C1-C6烷基；
    R 6、R 7、R 8、R 9各自独立地为氢、C1-C6烷基、C6-C12芳基或C7-C15芳烷基；或者R 6、R 7、R 8、R 9合起来形成饱和或不饱和的环，所述饱和或不饱和的环任选经C1-C6烷基取代；
    m 1、m 2、m 3、m 4各自独立地为1、2、3或者4；
    R 4、R' 4、R 5、R' 5各自独立地为氢或C1-C6烷基；
    a、b各自独立地为0、1、2、3、4或5，且Y为芳基或直连键时，a、b不为0。
  4. 根据权利要求1-3任一项所述的热固性环氧树脂组合物，其特征在于， 热固性环氧树脂组合物还包括催化剂；
    优选地，以所述组分A、组分B、组分C、组分D和组分E的总重量份数为100份计，所述催化剂的重量份数为0.001-5份，更优选为0.02-4份，进一步优选为0.05-3份；
    优选地，所述催化剂选自三级胺、三级膦、季铵盐、季鏻盐、有机金属络合物和咪唑化合物中的一种或至少两种的组合。
  5. 一种树脂胶膜，其特征在于，所述树脂膜由权利要求1-4任一项所述的热固性环氧树脂组合物经烘烤加热后半固化而成。
  6. 一种涂树脂铜箔，其特征在于，所述涂树脂铜箔是通过将权利要求1-4任一项所述的热固性环氧树脂组合物涂覆于铜箔上，并经由加热形成半固化态而得到。
  7. 一种半固化片，其特征在于，所述半固化包括增强材料，和通过含浸干燥后附着在所述增强材料上的如权利要求1-4任一项所述的热固性环氧树脂组合物。
  8. 一种层压板，其特征在于，所述层压板包括一张或至少两张叠合的如权利要求7所述的半固化片。
  9. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求7所述的半固化片，以及覆于一张半固化片或叠合后的半固化片的一侧或两侧的金属箔。
  10. 一种印制线路板，其特征在于，所述印制线路板是通过去除权利要求9所述的覆金属箔层压板表面的部分金属箔而形成电路的方法制得。
PCT/CN2020/082466 2019-12-26 2020-03-31 热固性环氧树脂组合物及使用其的半固化片、层压板和印制线路板 WO2021128630A1 (zh)

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CN114656749B (zh) * 2020-12-23 2024-03-29 广东生益科技股份有限公司 一种热固性树脂组合物及其应用
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