TW201127899A - Resin composition, and semi-solidification prepreg, laminated plate, and circuit board containing the same - Google Patents

Abstract

This invention discloses a resin composition mainly containing: epoxy resins, a curing promoter, a crosslinking agent, and a phosphorus-containing resin. The phosphorus-containing resin is a bisphenol novolak resin or novolak resin substituted by 9, 10-dihydro-9- oxa-10- phosphapheanthrene-10-oxide or derivatives thereof. The resin composition may be applied in the semi-solidification prepreg or circuit board insulating layer. Additionally, this invention also discloses a semi-solidification prepreg, laminated plate and circuit board containing the resin composition.

Description

201127899 VI. Description of the Invention: [Technical Field] The present invention relates to a resin composition, particularly a thermosetting resin composition which can be applied to a prepreg or a circuit board insulating layer, which mainly comprises a ring Oxygen resin, hardening accelerator, crosslinking agent and 9,10-dihydro-9-oxa-10-phosphaphenanthene oxide (9, 10-dihydro-9-oxa-lO-phosphaphenanthrene-10 - 〇xide, referred to as DOPO). [Prior Art] DOPO is a commonly used additive in a resin composition, and its main purpose is to improve the flame retardancy of the resin composition so that the resin composition can maintain stability even when it is applied to a high temperature environment. However, 'due to the poor reactivity of D〇p〇 with epoxy resin and cross-linking agent', the flame retardancy that can be achieved is still unsatisfactory. Therefore, in the prior art, 丨, 4-dual The phenol is attached to DOPO to form DOPO-HQ (HQ stands for hydroquinone ', ie hydroquinone), and its reactivity is enhanced by the introduction of a hydroxyl group. The Republic of China Patent Publication No. 1239973 discloses a flame-retardant resin composition modified by phosphorus and polydecane, which is reacted with an epoxy resin modified by d〇p〇_Hq and a poly-fine bond. . The Republic of China Patent Publication No. 1299352 discloses an adhesive containing a self-nuclear epoxy resin substituted by D0P0, which has high flexibility, moisture absorption and flame retardancy, and has a metal and plastic substrate. Good 201127899 followed by strength. In addition, the Republic of China Patent Publication No. 593526 discloses a phosphorus-containing compound having a DOPO or DOPO-UQ substituent and which can be used to form a flame-retardant 1 gas tree cured product for use as a packaging material and a printed circuit board. . SUMMARY OF THE INVENTION The main object of the present invention is to provide a resin composition mainly comprising an epoxy resin, a hardening accelerator, a crosslinking agent and a scaly resin, and the resin containing the resin is replaced by DOPO or a derivative thereof. Bisphenol novolac 'BPN' resin or phenolic nov〇iac (PN) resin. In terms of its characteristics, the resin composition provided by the present invention has substantially the characteristics of glass transition temperature, high heat resistance, flame retardancy, high shelf life, and the like, and can be applied to semi-cured film, metal foil laminate and circuit board. Wait. In the resin composition of the present invention, the phosphorus-containing resin preferably has the structure of the formula (I), the formula (II) or the formula (III): 201127899

OH formula (1)

Y

~~-~Y

w I Ph. I 2 OH

w IPh, I 2 OH

?H-P

W IPh, I 2 OH type (Π)

OH W Ph2 OH

?H

OH formula (III)

Wherein 'Phl Xiao Ph2 is a phenyl group, the via group (-OH) is linked to W in a para-position manner, and at least one of phi and Ph2 includes more than one X, and P h! and Ph 2 Each independently and selectively comprises more than one, .X is 9,10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof, selected from covalent bonds, aliphatic a functional group and an aromatic functional group; z from the A-month aliphatic functional group and an aromatic functional group; w is selected from the following H-fH, {Heart+. ., ;n is an integer greater than or equal to 丨. The J疋3 phosphorus resin is preferably a resin containing DOPO functional group 201127899 such as DOPO-PN (Formula 1) or DOPO-BPN, and wherein DOPO-BPN can be DOPO-BPAN (DOPO-bisphenol Anovolac, Formulas 2, 3) , DOPO-BPFN (DOPO-bisphenol F novolac, formula 4, 5), DOPO-BPSN (DOPO-bisphenol S novolac, formula 6, 7) and other alternative aldehyde compounds, as shown in the following formula: 201127899 OH C 〕 HC Vx λ formula (1)

7 201127899

201127899, wherein n is greater than or equal to an integer; 乂 is 〇〇1> 〇 functional group: Y is a covalent bond, an aliphatic functional group or an aromatic functional group; z is a nitrogen, an aliphatic functional group or an aromatic functional group . In addition, Μz may be bonded to the benzo ring-configuration of the substituent-substituent position, and each benzene ring is not limited to only one X or z substituent. For example, the benzene ring may have two or more X structures. Substituent, or having two or more z substituents. In addition, not every benzene ring structure needs to have a substituent, and it may also be a partial benzene ring structure.

^ has a X and Z substituent or both a z substituent and a part of the phenyl group has no X and Z substituents. Take DOPO-BPAN resin as an example, in which D〇p〇 functional system is bonded = BPAN resin with long chain and provides flame retardancy, while the base system on the moon is provided with its kind of resin (such as epoxy) Crosslinkability of resin). The BPAN of the long chain structure can provide a relatively uniform distribution of the DOPO functional groups bonded to the BPAN in addition to providing a plurality of via groups to crosslink with the resin thereof. Further, the preparation of the above various DOPO derivatives can be carried out by substituting D〇p〇 with a bisphenol phenol resin or a phenol resin, and further bonding a phosphorus atom of the compound to a carbon atom on the benzene ring. In the present invention, the phosphorus-containing resin has better flame retardancy than other kinds of phosphate compounds, and it has better crosslinkability than the D〇p〇 compound or the D〇P〇-HQ resin. It can increase the crosslinking density, reactivity and glass transition temperature '(4) to form a high Tg# material and improve the heat resistance stability of the resin composition. In the resin composition of the present invention, the epoxy resin preferably comprises at least 201127899 a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S (bisPhen〇l S) epoxy resin. Resin, phenacetal (phen〇in〇v〇lac) epoxy resin, bisphenol Anovolac epoxy resin, o-cresolnovolac epoxy resin, trifuncti〇nal epoxy Resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, epoxy resin, p-nonylbenzene ring Oxygen resin (p-xylene epoxy resin), naphthalene type epoxy resin, benzopyran epoxy resin, biphenyl novolac epoxy resin, phenolic phenylalkylphenol aldehyde (phen 〇i aralkyl novolac) epoxy resin or a combination thereof. Further, the epoxy resin is more preferably selected from the group consisting of a trifunctional epoxy resin, a tetrafunctional epoxy resin, and a polyfunctional epoxy resin, which can effectively improve the crosslinkability of each resin between the resin compositions, and can be further improved. The heat resistance of the resin and the mechanical strength after curing. In the resin composition of the present invention, the hardening accelerator is preferably selected from the group consisting of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methyl group. 2-methylimidazole (2MI), 2-phenyl-lH-imidazole (2ΡΖ), 2-ethyl-4-methyl η sit (2_ethyl-4-methylimidazole) , 2E4MZ), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), etc., or one or more of the Lewis test, or selected from violent, iron, drill, recorded One or more kinds of Lewis acids such as copper and zinc metal salt compounds. 201127899 In the resin composition of the present invention, the crosslinking agent preferably includes a diamino diphenyl sulfone (DDS) having high glass transition temperature, high heat resistance and high shelf life. The resin composition may further comprise at least one crosslinking agent selected from the group consisting of: a cyanate resin, a phenol resin, a phenolic resin (phenol novolac resin), styrene resin, polybutadiene resin, polyphenyl ether resin, anhydride compound, amine compound, and benzoxazine resin. Among them, the cyanate resin is a resin such as a cyanate ester or an isocyanate. The resin may be a hydroxyl group-containing resin such as dicyclopentadiene (〇1丨0>^1〇?61^(^116,00?0) type sulfonate resin. The amine-based crosslinking agent may be guanamine, Compounds such as dicyandiamide (DICY), diamino diphenyl methane (DDM), and bismaleimide (BMI). The acid anhydride compound may be methyltetrahydroxine ( Methyl tetrahydro phthalic anhydride 'ΜΤΗΡΑ), phthalic anhydride (PA), methyl dimethic acid glycol (NMA), styrene maleic anhydride (SMA), etc. In order to further improve the flame retardant properties of the resin composition, in the preferred case, at least one specific flame retardant compound may be selectively added to the present invention. The flame retardant compound selected may be a flame retardant salt. For example, the phosphate compound or the nitrogen-containing phosphate compound is not limited thereto. More specifically, the flame retardant compound preferably includes at least one of the following compounds: bisphenol diphenyl phosphate , polyamic acid ammonium [S] 11 201127 899 (ammonium poly phosphate), hydroquinone bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine, tri(2-carboxyethyl)phosphine, TCEP), tris(isopropyl chloride) sulphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), isophthalic bismuth Resorcinol dixylenylphosphate (RDXP (eg PX-200)), melamine polyphosphate (melamine)

Polyphosphate), phosphazene (such as SPB-1), azophosphorus compounds and their derivatives or resins, but not limited to this. Further, the resin composition of the present invention may further optionally contain an additive such as an inorganic filler, a surfactant, a toughening agent or a solvent. The main function of adding inorganic fillers is to increase the thermal conductivity of the resin composition and change it! The characteristics of thermal hybridity and mechanical strength, and the materials are preferably uniformly distributed in the tree remainder; the main purpose of adding the surfactant is to make the subtractive recordings all from the threats. The main purpose is to improve the resin composition. The physical properties; and Zhongtian: > Gu Xian main purpose is to change the viscosity of the fat composition of the tree residue. And adjust the tree, the inorganic filler may contain dioxide dioxide J), oxidation, oxidation town, magnesium oxychloride,: stone or: aluminum nitride, boron nitride, aluminum hydroxide, carbonization Ming... clay , titanium dioxide, zinc oxide, oxygen storage, quartz: cut, carbonated steel, graphite or calcined kaolin at least _, and ^ =, diamond-like powder, irregular type and optional shaft interface live, _ pre = can = [S] 12 “20 201127899 1, the following nano-sized granule powder can be the particle size (10) (four) below the end of the particle (four), and recorded as a granule / zm granule powder, the best particle size of the second end. " Amine The surfactant may comprise a Wei compound 1 oxy-sinter compound, a sulphate compound or a polymer of the above compound, etc. The attendant may comprise a solvent such as a rubber resin, a polybutadiene or a core-shell polymer, and may include methanol. Ethanol, ethylene glycol monomethyl, Ding'

Base ethyl ketone, methyl isobutyl _, cyclohexanone, toluene, xylyl ethyl acetate, ethoxyethyl acetate, propoxy ethyl acetate, acetamidine, A solvent such as mercaptoamine or propylene glycol decyl ether or a solvent thereof. And σ, in terms of the proportion of each main component of the composition, if the epoxy resin is 100 parts by weight, the preferred hardening accelerator is 〇〇〇1 to i parts by weight, and the side fat is 5 to _ parts by weight, and the crosslinking agent is 5 to 1 part by weight. Still another object of the present invention is to disclose a semi-cured film which has good flame retardancy, heat resistance stability, high glass transition temperature, halogen-free characteristics, and can be applied to an insulating layer material of a laminate and a circuit board. The semi-cured film of the present invention comprises the above-mentioned resin composition, wherein the resin composition is uniformly mixed by a mixing and agitating process, and then subjected to a heating process to form a semi-cured state. For example, the resin composition can be placed on a polyethylene terephthalate (PET) film and heated to form a semi-cured film. The purpose of the present invention is to disclose a laminate comprising at least [S3 13 201127899 a metal foil laminate and at least one insulating layer. The metal foil laminate may comprise a metal such as copper, aluminum, nickel, platinum, silver or gold or an alloy thereof, and is preferably a copper foil plate. The PET film is removed by bonding the semi-cured knee sheet disclosed in the present invention to at least one piece of the metal foil layer, and the semi-cured film and the metal foil layer are heated and solidified under high temperature and high pressure to form An insulating layer that is intimately bonded to the metal foil laminate. Still another object of the present invention is to disclose a half-cured film which has high mechanical strength, good flame retardancy, heat resistance stability, high glass transition temperature, and halogen-free characteristics. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and a resin composition as described above, wherein the resin composition is uniformly mixed after being mixed with the components through a mixing and stirring process, and then attached to the reinforcing material, and is subjected to high temperature. Heating forms a semi-cured state. Among them, the reinforcing material may be a fibrous material, a woven fabric, and a non-woven fabric, such as a glass fiber cloth, which can increase the mechanical strength of the semi-cured film. In addition, the reinforcing material may be optionally pretreated with a Xihua coupling agent or a 5 oxime coupling agent, such as a glass fiber cloth pretreated with a stagnation coupler. The aforementioned semi-cured film is formed into a cured film or a m-edge layer by heating at a high temperature or heating at a high temperature and under high pressure, wherein if the right composition of the resin composition has a 'treat agent', the solvent is volatilized and removed in a high-temperature heating program. . Yet another object of the present invention is to disclose a laminate comprising two or more metal box laminates and at least an insulating layer. The metal bismuth laminate may comprise a metal such as copper, nickel, face, silver or gold or an alloy thereof, and is preferably a slab: the insulating layer is formed by curing the above-mentioned half SHb# sheet under high temperature and pressure. 'Or the above-mentioned half-HI film 4 is combined with two metal 201127899 falling layers 2 and mixed with high temperature and high wealth. The laminates described in the second section have at least the following advantages: L flame retardancy, heat resistance stability, high surface resistance, excellent and halogen-free environmental protection. The layer of person/inside, mechanical strength: a circuit board can be formed after processing, and the system can be operated at high temperature and high humidity. # = i sub-joining. The further object of the present invention is to == without affecting quality. It has a heat-resistant ship, is resistant to _ characterization, $ = ' has its insulating layer and halogen-free characteristics, and is suitable for (4) problems and high mechanical strength. The circuit board of the circuit board is transmitted by a conventional circuit board process, and the present invention has the invention of the present invention to enable the person skilled in the art to which the present invention pertains. It is to be understood that the following is a further embodiment of the present invention. The following examples are intended to be illustrative of the invention, and are not intended to limit the scope of the invention, and It will be apparent to those skilled in the art that the invention may be practiced without departing from the spirit and scope of the invention. t A resin composition comprising the following components: (A) 100 parts by weight of a novolac epoxy resin (B) 30 parts by weight of DDS (C) 40 parts by weight of DOPO-BPAN resin [S] 15 201127899 (D) 0.1 parts by weight of decyl imidazole Example 2 A resin composition comprising the following components: (A) 100 parts by weight of bisphenol A epoxy resin (B) 40 parts by weight of benzene have been phenolic Novolac) resin

(C) 20 parts by weight of DDS (D) 20 parts by weight of DOPO-BPAN resin (E) 0.1 part by weight of dinonyl imidazole Example 3 A resin composition comprising the following components: (A) 100 parts by weight Dicyclopentadiene epoxy resin

(B) 30 parts by weight of DDS (C) 45 parts by weight of DOPO-BPAN resin (D) 50 parts by weight of molten cerium oxide (E) 1 part by weight of oxoxane compound (F) 50 parts by weight Base ethyl copper (G) 0.1 parts by weight of dimethylimidazole Example 4 A semi-cured film, the resin composition disclosed in Example 2 can be uniformly mixed in a stirring tank and then coated on a PET film. It is obtained by baking to a semi-cured state by heating. [s] 16 201127899 Embodiment 5 A semi-cured film, the resin composition disclosed in the third embodiment can be uniformly mixed in a stirring tank, placed in a dipping tank, and then the glass fiber cloth is passed through the impregnation tank. The resin composition is adhered to a glass fiber cloth and baked and baked in a semi-cured state. Embodiment 6 A laminate comprising a half-cured film, a copper foil and a circuit substrate, wherein the semi-cured film is bonded to the circuit substrate by the plane of the pre-cured film without the PET film, as described in Embodiment 4. The PET film is removed, and one side of the pre-cured film is removed from the PET film and bonded to a copper foil, and then pressed at a high temperature and a high pressure to cure the semi-cured film to form an insulating layer between the copper foil and the wiring substrate. Embodiment 7 A laminate comprising four semi-cured films and two copper foils according to the fifth embodiment, laminated in the order of copper foil, four semi-cured films, and copper foil, and then subjected to high temperature and high pressure processes Pressing causes the four sheets of prepreg to cure to form an insulating layer between the two copper foils. Embodiment 8 A circuit board comprising a plurality of laminates and a plurality of prepreg films, wherein the laminates are laminated according to the seventh embodiment and then subjected to a photolithography process to form a surface circuit, and the semi-cured film is implemented. In the fifth embodiment, the plurality of [S] 17 201127899 laminates are interposed between the plurality of prepreg films and the two copper foils, and the laminated structure further forms a circuit board substrate by a south temperature and high pressure pressing process. The circuit board substrate can be fabricated into a circuit board by a conventional circuit board processing process, and will not be described here. Embodiment 9 A circuit board 'the main structure is as described in Embodiment 8, except that the laminated board is further subjected to a drilling process to form a blind hole. Comparative Example In addition, three different resin compositions were prepared for comparing the different phosphorus-containing compounds in the composition to the composition of the composition: epoxy resin hardening accelerator cross-linking phosphorus-containing compound composition A phenolic epoxy resin 100 parts by weight of dimethylimidazole 0.1 parts by weight of DDS 30 parts by weight of D0P0-BPAN 40 parts by weight of composition B TMP 40 parts by weight of composition C DOPO 40 parts by weight of the above resin compositions A, B and C according to Example 5 and Example 7 In the above step, an insulating substrate is formed, and the substrate containing the resin compositions A, B, and C is respectively measured for solder dip, heat resistance, flame resistance, water absorption, rigidity, glass transition temperature, and heat resistance after water absorption ( Pressure [S3 18 201127899 cooking test], the test results show that compared with the insulating substrate formed by the composition A containing DOPO-BPAN, the insulating substrates formed by the compositions B and C all have a low glass transition temperature, and the water absorption thereof It is rigid, flame-resistant, and heat-sensitive and heat-sensitive after water absorption. [Simple description of the diagram] No 0 [Description of main component symbols] None.

Claims (1)

201127899 VII. Patent application scope: 1. A resin composition, including: epoxy resin; hardening accelerator; cross-linking agent; and lining resin, which is 9,10-diaza-9-milk-10- A bisphenol phenolic resin or a phenolic resin substituted with a scale/phenanthrene-10-emulsifier or a derivative thereof. 2. The resin composition according to claim 1, wherein the phosphorus-containing resin has a structure of the formula (I), the formula (Π) or the formula (ΠΙ): OH OH OH 0H | OH | OH | Ph, Y Ph, -Y——Ph, 1 1 W 1 ww I Ph9 Ph2 Ph2 OH OH OH n OH 1 — OH | Ph,—— I 1 Y Ph, w | w I OH Ph2 Ph, — 1 2 Y Ph, OH OH w η I π OH Formula (1) Formula (II) Formula (III) wherein, Ph and Ph2 are both phenyl groups, and the hydroxyl groups thereon are linked to W in a para-position. At least one of Phi and Ph2 includes more than one X, and the Ph! and Ph2 systems each independently and selectively include more than one [S] 20 201127899 m [10· Dihydrogen oxalate, · Phosphorus phenanthrene-ι〇 - an oxide or a derivative thereof derived from a covalent bond, an aliphatic functional group and an aromatic functional group; a z-chain oxygen; an energy group and an aromatic functional group; and a W system selected from the following H. «CC-CH, HCH HX-C -<〇)〇+◦ CK ; η is an integer greater than or equal to i. The resin composition described in the above, wherein the epoxy resin ring eucalyptus i, F epoxy resin, S is made of τ rolling tree and phenol phenolic phenolic epoxy resin, o-cresol = two t, difunctional epoxy Resin, tetrafunctional epoxy resin, multi-official: Ityue, bicyclononadiene cyclic oxime resin, phosphorus-containing cyclic oxime resin, p-oxime enamel resin, naphthalene epoxy resin Τ: Γ Oxygen=:, the tree m&s product described in item 1 of the month, the towel hardened 2: two from: saliva, boron trifluoride complex, chlorinated ethyltriphenyl scale, earthy saliva, 2-Phenyl sulphate, 2_ethyl _4•methyl saponin, :: Γ^^ 5:: The resin composition described in Item 1 of the ί利范围, in which the crosslinking agent is packaged Makeup base two stupid sulfone. 6. The resin composition according to claim 5, further comprising at least one 201127899 cross-linking agent selected from the group consisting of: a cyanate tree, a phenol resin, a phenolic resin Resin, styrene resin, polybutadiene resin, 7 polyphenylene ether resin, acid anhydride compound, amine compound, and benzophthalocyanine resin. The resin composition as claimed in claim 1, further comprising a flame retardant compound selected from the group consisting of: dipyridic acid-acid, ammonium polyphosphate, and para-benzene Diphenol-bis-(diphenylphosphate), tris(2-carboxyethyl), di(isopropyl chloride) acid, triterpene acid salt, dimethyl methacrylate Isophthalene is expected to be a bis-xylene-acid salt, a s-acid, a nitrogen-based compound, and a argon-filled compound. • The resin composition as described in claim 1 further comprises at least one = 'inorganic filler from the following group or a combination thereof: cerium oxide, [: magnesium oxide, magnesium hydroxide, calcium carbonate, talc , ^ delete, hydrogen oxygen her, carbonized wealth, carbon cut, sodium carbonate dioxification of kaolin.匕 、, 氧化 、, quartz, diamonds, diamond-like, graphite, cannon burning 9 · = 专利 composition of the scope of the _ composition, including at least -10 '丨 surfactant, toughener, solvent Or a combination thereof. The resin composition described in the first item of the patent range, wherein the epoxy resin is 100 parts by weight, the hardening accelerator is 0.001 to i 〇, and the phosphorus-containing resin is 5 to 30. The parts by weight and the cross-linking agent are 5 to (10) liters of U's two kinds of prepreg films, and the resin composition as described in the above-mentioned U.S. Patent Application Serial No. Ui, wherein the resin composition is in a semi-cured state. 22 [S] 201127899 12. The semi-cured film of claim 11, further comprising a glass fiber cloth coated with a semi-cured resin composition. 13. A laminate comprising at least one metal II laminate and at least one insulating layer formed by curing the prepreg according to any one of claims 11 to 12. A circuit board comprising at least one laminate as described in claim 13 of the patent application. 201127899 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201127899 Invention patent specification year 4·month 2 补 Correction (The format and order of this manual, please do not change it arbitrarily, please do not fill in the ※ part) ※Application Case No. ※Application: 99 1 04777 99. 2 Name of the invention: (Chinese / English) ※Working PC classification: * % Ο Resin composition and semi-cured film, laminate and circuit board containing the resin composition, Chinese invention Abstract: cl -- The resin disclosed herein is a resin composition mainly comprising an epoxy resin on hardening accelerator, a crosslinking agent and a phosphorus-containing resin, which is a 9,10-dihydro-9-oxygen. A bisphenol phenolic resin or an aged acid resin substituted with a hetero-10-phosphaphenanthrene-10-oxide or a derivative thereof. The resin composition can be applied to a semi-cured film or a circuit board insulating layer. Further, a prepreg film, a laminate, and a circuit board containing the resin composition are also disclosed herein. III. English Abstract: 201127899, invention: [Technical field of invention] j The present invention relates to a resin composition, in particular to a thermosetting resin composition which can be applied to a prepreg or a circuit board insulating layer. 'It mainly contains epoxy resin, hardening accelerator, cross-linking agent and 9,10-hydrogen-9-oxa-phosphonium-phosphonium oxide (9, 10 dihydro 9-〇xa) -l〇-ph〇Sphaphenanthrene -10-oxide, referred to as D0P0) is replaced by a phosphorus-containing resin. [Prior Art] D0P0 is a commonly used additive in a resin composition, and its main purpose is to improve the flame retardancy of the resin composition so that the resin composition can maintain stability even when applied to a high temperature environment. However, 'due to the poor reactivity of DOPO with epoxy resin and cross-linking agent', the flame retardancy that can be achieved is still unsatisfactory. Therefore, in the prior art, it was proposed to attach K-dihydroxyphenol to DOPO. To form dopo-hq (hq for hydr〇quinone, hydroquinone), the reactivity is improved by the introduction of a hydroxyl group. The Republic of China Patent Publication No. 1239973 discloses a flame-retardant resin composition modified by phosphorus and polysulfide, which is reacted with a polydecane bond by a D〇p〇_hq-modified epoxy resin. Got it. The Republic of China Patent Publication No. 1297352 discloses an adhesive containing a halogen-free epoxy resin substituted by D〇P〇, which has high flexibility, moisture absorption resistance and flame retardancy, and is metal-based and plastic-based. The material has a good 201127899 followed by strength. In addition, the Republic of China Patent Publication No. 593526 discloses a compound containing a DOPO or DOPO-HQ substituent and which can be used as a packaging material and a printed circuit board. SUMMARY OF THE INVENTION The main object of the present invention is to provide a resin composition mainly comprising an epoxy resin, a hardening accelerator, a crosslinking agent, and a phosphorus-containing resin, and the phosphorus-containing compound is derived from DOPO or derived therefrom. a bisphenol novolac ' ΒΡΝ resin or a phenolic acid (phen 〇 1 η 〇 〇 ,, (4) resin. The resin composition provided by the present invention has substantially the same glass = glass transition Temperature, high heat resistance, flame retardant, and can be applied to semi-cured film, metal box laminate and circuit board riding in the present invention, containing phosphorus tree (four) ^ (1), formula (II) or Structure of formula (III): U type 201127899 OH I -ΡΙγ I 1 w I ?H Y-Ph, i 1 W I Ph, i 2 OH Formula (i) ?H ?hi w Formula (II) OH Ph2 OH 0Η 1 OH ~Y--Ph, WI 1 IW i Ph2- OH I 2 OH OH Y——phl w IPh, i 2 OH Formula (III) O is phenyl at 114% The radical (-OH) is relative to the above X, and is Γ-linked, at least one of % and % includes - and the z hl and % are each independently and selectively include more than one; The oxaloin 1 ΰ (5) phenanthrene oxide or a derivative thereof is selected from the group consisting of a hydrogen dialiphatic functional group and an aryl (tetra) functional group; Ζ group: "a fatty functional group and an aromatic functional group; W is selected from the following H3C- C^ch3 h4-h kc4 0=S=:〇 H»C—C-CH„ , 11 is an integer greater than or equal to i. The 含's squaring resin is preferably a resin containing a ruthenium functional group, 201127899 such as DOPO-PN (Formula 1) or DOPO-BPN, And wherein DOPO-BPN can be DOPO-BPAN (DOPO-bisphenol A novolac, formulas 2, 3), D〇PO-BPFN (DOPO-bisphenol F novolac, formula 4, 5), DOPO-BPSN (DOP〇-bisphenol S Novolac, formula 6, 7) and other bisphenol phenolic compounds, as shown in the following formula: 201127899 7 201127899 201127899 wherein n is an integer greater than or equal to 1; X is a DOPO functional group: Y is a covalent bond, an aliphatic functional group or an aromatic functional group; and z is a nitrogen 'aliphatic functional group or an aromatic functional group. In addition, X and Z may be bonded to the benzene ring, the #* substituent position on the mouth structure, and each benzene ring is not limited to only one X or z substituent. For example, there may be two benzene ring structures. Or an X substituent above, or two or more z substituents. In addition, not every benzene ring has a X and z substituent, and may also have a X and Z substituent or a χ#ζ substituent on a part of the benzene ring structure, and a part of the benzene ring structure. Does not have X and oxime substituents. Take DOPO-BPAN resin as an example, in which the D0P0 functional group is bonded. It has a long-chain structure and provides flame retardancy, while the 3 chest tree and the fat-based system provide it with its kind of resin (such as epoxy). Crosslinkability of resin) 3. The removal of the long-chain structure provides a cross-linking effect between the multi-featured group and the lysine. The bonding to the BPANUOPO functional group will result in a more uniform resin structure. ^ ^ ’ ’ The preparation of the above various derivatives of DQPO can be carried out by substituting with a bisphenol phenol resin or a phenol resin to bond the carbon atoms of DOPO with the carbon atoms on the benzene ring. + In the present invention, the lining resin has better flame retardancy than other types of sulphated acidified persons, and it has better crosslinkability than the DOPO compound or the DOPO-HQ resin. Crosslink density, reactivity and glass transition temperature, which in turn form high Tg materials and improve: heat stability. The epoxy resin preferably comprises at least 201127899 a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S (bisphenol S). S) Epoxy resin, phenolic (phen〇l nov〇iac) epoxy resin, double-aged bisphenol Anovolac epoxy resin, o-cresolnovolac epoxy resin, trifunctional (trifuncti〇nal Epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-pair P-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenyl novolac epoxy resin, phenolic phenyl benzene A phenolic aldehyde (such as aralkyl novolac) epoxy resin or a combination thereof. In addition, the epoxy resin more alumina is selected from the group consisting of a trifunctional epoxy resin, a tetrafunctional epoxy resin, and a polyfunctional epoxy resin, which can effectively improve the cross-linking of each resin between the resin compositions, and The heat resistance of the resin and the mechanical strength after curing can be further improved. In the resin composition of the present invention, the 'hardening accelerator is preferably selected from the group consisting of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methyl port. 2-methylimidazole (2MI), 2-phenyl-lH-imidazole (2PZ), 2-ethyl, 4-methyl for saliva (2-ethyl-4-methylimidazole, 2E4MZ ), one or more of the triphenylphosphine (TPP), 4-dimethylaminopyridine 'DMAP, etc., or selected from the group consisting of fierce, iron, cobalt, nickel, copper And one or more Lewis acids such as a zinc metal salt compound. 201127899 In the resin composition of the present invention, the crosslinking agent preferably includes diamino diphenyl sulfone (DDS), which has high glass transition temperature, high heat resistance and high shelf life. Effectively improving the cross-linking and curing action of the epoxy resin; furthermore, the 'resin composition may further comprise at least one cross-linking agent selected from the group consisting of the following: a cyanate resin, a benzoate resin, A phenol novolac resin, a styrene resin, a polybutylene resin, a polyphenyl ether resin, an anhydride compound, an amine compound, and a benzoxazine oxime resin. Among them, the cyanate resin is a resin such as a cyanate ester or an isocyanate. The resin may be a hydroxyl group-containing resin such as a dicyclopentadiene (DCPD) type platter resin. The amine-based crosslinking agent may be a compound such as decylamine, dicyandiamide (DICY), diamino diphenyl methane (DDM), or bismaleimide (BMI). The acid anhydride compound may be methyl tetrahydro phthalic anhydride (ΜΤΗΡΑ), phthalgf (phthalic anhydride, PA), nadic methyl anhydride (NMA), styrene. A compound such as styrene maleic anhydride (SMA). In order to further improve the flame retardant properties of the resin composition, in the preferred embodiment, the present invention may optionally additionally add at least one specific flame retardant compound. The flame retardant compound selected may be a flame retardant salt such as a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto. More specifically, the flame retardant compound preferably includes at least one of the following compounds: bisphenol diphenyl phosphate, ammonium polyphosphate 11 201127899 (ammonium poly phosphate), hydroquinone-double -(biphenyl chloride), tri(2-carboxyethyl)phosphine (TCEP), tris(isopropyl) sulphate, Trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), benzoic acid dixylenyl phosphate (RDXP) Such as ΡΧ-200)), melamine polyphosphate, scalar nitrogen compounds (ph〇Sphazene, such as SPB-100), chlorhexidine nitrogen compounds and their derivatives or resins, but Not limited to this. Further, the resin composition of the present invention may further optionally contain an additive such as an inorganic filler, a surfactant, a toughening agent or a solvent. The main function of adding the inorganic filler is to increase the thermal conductivity of the resin composition, which is good in thermal occupation and difficult to be mixed, and the inorganic filler is preferably uniformly distributed in the excess of the tree; the addition of the surfactant is The inorganic filler wire can be (4) dispersed in the tree mash; the addition is to improve the resin composition and add the fat composition. In (4), the composition of the 13 content of the composition, and adjust the inorganic filler in the tree can be ordered - / μ work f h state), oxidation, magnesium oxide ... V melt or non-glare aluminum nitride, boron nitride. Wind emulsified magnesium, calcium carbonate, talc, clay, rolled boron, lanthanum alumina, titanium dioxide, zinc oxide, oxidized A, sodium carbonate, graphite or calcined kaolin * diamond powder, zanzan powder, irregular type, and The inorganic filler may be spherical or alternatively pretreated via an interfacial surfactant. Inorganic filling 201127899 The material may be a granular powder having a particle diameter of 100 Å or less, and is preferably a granule powder of a granule-pinch (four), preferably a nano-sized powder having a particle diameter of 四(iv) or less. The knife interfacial surfactant may comprise a zephyr compound, an aurora compound, an amino decane compound or a polymer of the above compound. The additive blade may comprise a solvent such as a rubber resin, a polybutanide or a core-shell polymer, and may include methanol, ethanol, ethylene glycol monoterpene ether, top, oxime ethyl ketone, methyl isobutyl ketone. , cyclohexanone, toluene, diphenylbenzene, methyl acetophene ethyl hydrazine, ethoxyethyl acetate vinegar, propoxyethyl acetate 酉: ethyl acetate, dimethyl acetamide, propylene glycol A solvent such as methyl ether or a solvent thereof. Q. In terms of the proportion of each of the main components of the composition, if the epoxy resin is used in an amount of 1.0 part by weight, the curing accelerator is preferably 0.001 to 1.0%, and the phosphorus-containing resin is 5 to 300 parts by weight, and the crosslinking agent is 5 parts by weight. Still another object of the present invention is to disclose a semi-cured film which has good flame retardancy, heat resistance stability, high glass transition temperature, no Nancel, and the like, and can be applied to an insulating layer of a laminate and a circuit board. material. The semi-cured film of the present invention comprises the above-mentioned resin composition, wherein the resin composition is uniformly mixed by a mixing and agitating process, and then subjected to a heating process to form a semi-cured state. For example, the resin composition can be placed on a film of polyethylene terephthalate (PET) and heated to form a prepreg. A further object of the present invention is to disclose a laminate comprising at least 13 201127899 a metal pig laminate and at least one insulating layer. The metal pig laminate may comprise a metal such as copper, Ming, Lu, Ming, Silver, or gold or an alloy thereof, and is preferably a copper foil plate. The PET film is removed by laminating the semi-cured film disclosed in the present invention on at least one piece of the metal foil layer, and the semi-cured rubber and the metal foil layer are heated and solidified under high temperature and high pressure to form and The metal foil laminate is intimately bonded to the insulating layer. Still another object of the present invention is to disclose a half-cured film which has high mechanical strength, good flame retardancy, heat resistance stability, high glass transition temperature, and halogen-free characteristics. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and a resin composition as described above, wherein the resin composition is uniformly mixed after being mixed with the components through a mixing and stirring process, and then attached to the reinforcing material, and is subjected to high temperature. Heating forms a semi-cured state. Among them, the reinforcing material may be a fibrous material, a woven fabric, and a non-woven fabric, such as a glass fiber cloth, which can increase the mechanical strength of the semi-cured film. Further, the reinforcing material may be optionally pretreated with a decane coupling agent or a decane coupling agent such as a glass fiber cloth pretreated with a decane coupling agent. The aforementioned prepreg film can be cured by high temperature heating or high temperature and high pressure to form a cured film or a solid insulating layer. If the resin composition contains a solvent, the solvent is volatilized and removed in a high temperature heating process. It is still another object of the present invention to disclose a laminate comprising two or more metal foil laminates and at least one insulating layer. The metal foil laminate may comprise a metal such as copper, indium, nickel, flip, silver, gold or the like, and is preferably a copper foil plate: the insulating layer is cured by the aforementioned prepreg film under high temperature and high pressure. Alternatively, the prepreg film is laminated between two metal 14 201127899 berth plates and pressed under high temperature and high pressure. The laminate described in this July has at least one of the following advantages: heat-resistant flame retardancy, heat-resistant stability > Guangliang's Chengli kiss-shaped laminate is advanced by making lines, etc., and 5 Hai circuit board and electronics After the components are picked up by your coffin for high temperature and high thirst, the invention will not be affected by the quality of the second generation. Ο It has the difficulty of heat resistance, the resistance to the transition layer, the conversion temperature of the special glass, and the high mechanical strength. In the middle, the high-speed and high-frequency signal transmission circuit board can be made by the conventional circuit board process: the layer "reverse" and the [embodiment] clarifies the invention. However, the following is a step-by-step description of several embodiments. The following embodiments are only used to the present invention, and are not intended to limit the scope of implementation of the present invention, and any of the finer =::: domain has the usual knowledge of the present invention. - Modifications and variations, which fall within the scope of the invention, include the following components: (A) 100 parts by weight of phenolic epoxy resin (8) 30 parts by weight of DDS (C) 40 parts by weight of D〇P〇-BPAN resin 15 201127899 (D) 0.1 parts by weight of decyl imidazole Example 2 A resin composition comprising the following components: (A) 100 parts by weight of bisphenol A epoxy resin (B) 40 parts by weight of benzoquinone (phenolic novolac) resin (C) 20 parts by weight of DDS (D) 20 parts by weight of DOPO-BPAN resin (E) 0.1 part by weight of dinonyl imidazole Example 3 A resin composition comprising the following components: (A 100 parts by weight of dicyclopentadiene epoxy resin (B) 30 parts by weight of DDS (C) 45 parts by weight of DOPO-BPAN resin (D) 50 parts by weight of molten cerium oxide (E) 1 part by weight of a siloxane compound (F) 50 parts by weight of decylethyl copper (G) 0.1 Dimensions of dimethyl squirting Example 4 A semi-cured film, the resin composition disclosed in the second embodiment can be uniformly mixed in a stirring tank and then coated on a PET film and heated for baking. 16 201127899 Example 5 A semi-cured film, the resin composition disclosed in the third embodiment can be mixed in a stirring tank and placed in a dipping tank, and then the glass fiber cloth The resin composition is adhered to the glass fiber cloth by the impregnation bath and heated and baked into a semi-cured state. Embodiment 6 A laminate comprising a half-cured film, a copper box and a line substrate, wherein The semi-cured film is as described in the fourth embodiment, the plane of the pre-cured film without the PET film is combined with the circuit substrate, the PET film is removed, and the semi-cured film is removed from one side of the PET film and a copper foil. Bonding, then through high temperature and high pressure The semi-cured film is cured to form an insulating layer between the copper foil and the circuit substrate. Embodiment 7 Q A laminate comprising four semi-cured films and two copper foils according to the fifth embodiment, according to copper foil, The four sheets of semi-cured film and copper foil are laminated in the same order, and then pressed by a high temperature and high pressure process, so that the four sheets of semi-cured film are cured to form an insulating layer between the two copper foils. The laminates and the plurality of semi-cured rubber sheets, wherein the laminates are laminated according to the seventh embodiment, and then through a lithography process to form a surface circuit, the semi-cured film is as described in the fifth embodiment, the plurality of 17 201127899 The laminate and the plurality of semi-cured films are interlaced between the two copper foils, and the laminated structure is further formed into a circuit board substrate by a high temperature and high pressure pressing process, and the circuit board substrate can be fabricated through a conventional circuit board processing process. Form a circuit board, not to repeat here. Embodiment 9 A circuit board having a main structure as described in Embodiment 8 except that the laminated board is further subjected to a drilling process to form a blind hole. Comparative Example In addition, in order to compare the influence of different phosphorus-containing compounds in the composition on the physicochemical properties of the composition, three different resin compositions were prepared according to the following table: Epoxy resin hardening accelerator cross-linking compound composition A D0P0-BPAN 40 parts by weight of the composition B phenolic epoxy resin 100 parts by weight of dimercapto 13 meters 嗤 0.1 parts by weight of DDS 30 parts by weight of TMP 40 parts by weight of the composition C DOPO 40 parts by weight of the above resin compositions A, B and C according to the fifth embodiment The steps described in the seventh embodiment are performed to form an insulating substrate, and the substrates containing the resin compositions A, B, and C are respectively measured for solder heat resistance, flame resistance, water absorption, rigidity, glass transition temperature, and heat resistance after water absorption. Test (pressure 18 201127899 cooking test), the test results show that compared with the insulating substrate formed by the composition A containing DOPO-BPAN, the insulating substrates formed by the compositions B and C have a lower glass transition temperature, and the water absorption thereof Sex, rigidity, flammability, heat resistance and heat resistance after water absorption are poor. [Simple description of the schema] Benefits. [Main component symbol description] None. 19 201127899 Invention patent specification year 4·Month 2 补 Correction (The format and order of this manual should not be changed at any time, please do not fill in the ※ part) ※Application number ※Application number: 99 1 04777 99. 2 Name of invention: (Chinese /English) ※Working PC classification: * % Ο Resin composition and semi-cured film, laminate and circuit board containing the resin composition, Chinese Abstract: cl -- The person disclosed here is a resin composition, mainly The invention comprises an epoxy resin on hardening accelerator, a crosslinking agent and a phosphorus-containing resin, which is replaced by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof. The bisphenol phenolic resin or the aged resin' resin composition can be applied to a semi-cured film or a circuit board insulating layer. Further, a prepreg film, a laminate, and a circuit board containing the resin composition are also disclosed herein. III. English Abstract: 201127899 VII. Patent Application Range: 1. A resin composition, including: epoxy resin; hardening accelerator; cross-linking agent; and phosphorus-containing resin, which is 9,10-dihydro-9 a bisphenol phenolic resin or a phenolic resin substituted with an oxa-yt-phosphaphenanthene oxide or a derivative thereof. The resin composition of claim 1, wherein the scaly resin has the structure of formula (I), formula (Π) or formula (III): OH Y OH I Formula (I) Formula (II) ihH w Ph2- OH OH Y——Ph, w I Ph2 OH Formula (III) /, Phh! and Ph2 are both phenyl groups, and the base system is relatively Connected in w to the para position, at least one of phl and Ph includes more than one X, and Phl and ph2 are each independently and selectively include more than one 20 201127899 Z; X is 9,10-dihydro-9 - oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof; Y is selected from the group consisting of a covalent bond, an aliphatic functional group, and an aromatic functional group; and the Z system is selected from the group consisting of hydrogen, an aliphatic functional group, and an aromatic functional group. Base; W is selected from the following groups: ; η is an integer greater than or equal to 1. 3. The resin composition according to claim 1, wherein the epoxy resin comprises at least one bisphenol oxime epoxy resin, bisphenol F epoxy resin, bisphenol S, epoxy resin, novolac epoxy resin, Bisphenol A phenolic epoxy resin, o-nonyl phenol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, polyfunctional epoxy resin, dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin , p-terephthalic epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenol novolac epoxy resin, phenolic phenyl alkyl novolac epoxy resin or a combination thereof. 4. The resin composition according to claim 1, wherein the hardening accelerator is selected from the group consisting of imidazole, boron trifluoride complex, ethyltriphenyl chloride, 2-mercaptoimidazole, 2- Phenyl imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-didecylaminopyridine, and metal salt compounds of manganese, iron, cobalt, nickel, copper, and zinc. 5. The resin composition of claim 1, wherein the crosslinking agent comprises diaminodiphenyl hydrazine. 6. The resin composition as claimed in claim 5, further comprising at least one cross-linking agent of 21 201127899, a modified substance thereof or a combination thereof: cyanate vinegar: diphenol resin, Phenolic resin, styrene resin, polybutadiene resin, polystyrene, acid compound, amine compound, and benzophthalocyanine resin. 7. If you apply for a patent scope! The resin composition described in the above, further comprising at least - 1 selected from the group consisting of flame retardant compounds or a combination thereof: Weilian benzoic acid: polycylic acid, p-benzene H (diphenylde salt), Tris(tetra)ethinyl)phosphine, tris(isopropyl chloride) sulphate, tridecyl phosphate, dimethyl-methyl phosphate, isophthalic acid bis-diphenyl phenyl phosphate, melamine polyphosphate , phosphorus-nitrogen compounds and azo-phosphorus compounds. 8. The resin composition described in the first paragraph of the patent scope, further comprising at least - I. Inorganic filler or its combination: dioxygenation, oxidation: magnesium: magnesium hydroxide, calcium carbonate, talc, clay , nitrided, =,, riding, immortalization, carbonization _, carbon cutting, carbon axis, oxidized kaolin, oxidized, quartz, diamond, diamond-like, graphite, calcined two:: patent scope 8 The resin composition described further includes at least a " surfactant, toughening agent, solvent or a combination thereof. The resin composition described in the first item of the Hi patent range, wherein the epoxy refers to the weight of the hardening portion of the 'hardening-promoting sword to the coffee to the weight: ": part-to-weight portion, the crosslinking agent is 4 u · A semi-cured film, including as claimed in the patent: =: r thing's - system: 22 201127899 12. The semi-cured film as described in the scope of claim 5, further comprising a semi-cured m resin composition Covered glass fiber cloth. 13. A laminate comprising at least one metal box laminate and at least one insulating layer, wherein the insulating layer is formed by curing a semi-cured film of any of the items _ u to 丨 2 . And a circuit board comprising at least one laminate as claimed in the patent. Scope item 13 〇 23 201127899 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: