TW201136982A - Halogen-free flame retardant resin composition - Google Patents

Abstract

The present invention provides a halogen-free flame retardant resin composition including: (A) epoxy resin; (B) phosphorus-containing phenolic resin curing agent; (C) chain extension agent; and (D) inorganic filling powder that can be selectively added. By using specific phosphorus-containing phenolic resin curing agent, this invention can further achieve the purposes of having excellent flame-retardant and heat tolerant properties, high dimensional stability, low hygroscopicity, excellent electrical property and excellent processing property.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant resin composition, and more particularly to a composition of a non-halogen flame-retardant resin using a phosphorus-containing phenolic resin hardener. [Prior Art] In response to the world's green insurance trend and the green regulation 'Halogen-free' is the current environmental trend of the global electronics industry, countries around the world and related electronics companies have developed halogen-free electronic products for their electronic products. Mass production schedule. European Union Restriction of Hazardous Restriction

After the implementation of Substances, RoHS, substances such as lead, cadmium, mercury, hexavalent chromium, polybromine, and polybrominated diphenyl ethers have not been used to manufacture electronic products or their components. Printed Circuit Board (PCB) is the basis of electronic motor products. The toothless printed circuit board is also the first target of control. 'International organizations for printed circuit boards!|The content of the element has strict I requirements' Among them, the International Electrotechnical Commission (mc) 61249_2_21 requires bromine and chloride content to be less than 9〇〇ppm, and the total halogen content must be less than 1500 ppm. The 电子本电子电路工业会 (JPCA) regulates bromide and vaporization. The content limit is 900 ppm; and Greenpeace's greening policy, which is strongly promoted at this stage, requires all manufacturers to completely eliminate the polyethylene and bromine flame retardants in their electronic products to meet both lead-free and halogen-free. Green electronics. Therefore, the halogen-free material has become a key development project for the current industry. Epoxy resin is excellent in adhesion, heat resistance, and formability. Therefore, it is widely used in electronic components and motor machinery. From the viewpoint of safety against fire, the material is required to have flame retardancy, and is generally made of a flame retardant epoxy resin in combination with an external tanning agent to achieve a flame retardant effect, for example, in a ring gas resin. A halogen, especially bromine, is introduced to impart flame retardancy and increase the reactivity of the epoxy group. However, recently, electronic products tend to be lightweight, miniaturized, and circuit miniaturized. Under such requirements, a relatively large halide is not preferable in terms of weight reduction. In addition, after being used for a long period of time at a high temperature, it may cause the dissociation of the _ compound and the fine wiring is rotted. In addition, the used electronic components after use will produce harmful compounds such as ruthenium compounds after combustion, and are not friendly to the environment. In order to replace the above-mentioned toothed flame retardant, it has been studied to use a phosphorus compound as a flame retardant', for example, a phosphate ester (Republic of China Patent Publication No. ι238846) or red phosphorus (Republic of China Patent No. 322507) in an epoxy resin composition. . However, 'phosphate esters will cause acid hydrolysis due to hydrolysis reaction, which will affect its migration. The red phosphorus has high flame retardancy, but it is referred to as dangerous goods in the fire protection law, because it will be in high temperature and humid environment. A trace amount of phosphine gas occurs. Therefore, there have been studies to improve the above-mentioned disadvantages, and to introduce a flame-retardant group into a compound or a polymer structure in a bonding manner to improve flame retardancy, for example, 'Japanese Patent Publication No. 2002-302529, 2005-67095 No. 2006-342217, which discloses the modification of an organic cyclic phosphorus compound (9, ίο-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as HCA or DOPO) as a halogen-free A flame retardant in a resin composition. 201136982 Use a specific type of (4) __ composition, by using the special resin hard characteristics, and improve the _ circuit board can be a good flame retardant. (10) Adding H will be the present invention. [Invention] In view of the above-mentioned conventional lining epoxy resin

Temperature (Tg) is not easy to reach, invention = production, ^ Yu Yuanshan' exhausted his mind to study and overcome, based on its accumulated experience, and then developed - (4) riding resin hardening 揪: its none A refractory resin composition of dentin in order to achieve good flame retardant properties. The main object of the present invention is to provide a halogen-free flame-retardant resin composition which achieves good flame retardant properties, dimensional stability, low hygroscopicity, good electrical properties by using a specific phosphorus-containing phenolic resin hardener. Good processing characteristics and / or good heat dissipation characteristics. In order to achieve the above object, the present invention provides a dentate-free flame retardant resin composition comprising: (A) an epoxy resin; (B) a linonic acid/resin hardener; and (c) a chain extender. The above composition 'optionally adds (D) an inorganic filler powder. The above composition, wherein the component (B) is a compound of the following formula (1), a compound of the formula (1): 201136982

Wherein n and m are both 0 or 1, and when it is 0, it represents that the chemical bond is hydrogen; hydrazine is hydrogen or alkyl; HCA is a compound of the following formula (2), a compound of formula (2):

0 = P-0 wherein R2 is a substituted or unsubstituted alkylene group of 0 to 5 carbons. In the above composition, the component (B) has a molecular weight of 700 to 2200 g/mol and a phosphorus content of 5 to 12%, and can be mixed with a plurality of different epoxy resins to easily achieve a flame retardant effect. Further, in a preferred case, the phosphorus-containing phenolic resin hardener of the component (B) may be physically added or chemically incorporated into a specific inorganic component, such as Shi Xi, and the ratio may be 0.1 to 3%. The above composition, wherein the component (A) is selected from one of a bisphenol type epoxy resin, a novolac type epoxy resin, a tetrafunctional epoxy resin, and a phosphorus-containing epoxy resin, or a combination thereof. 201136982 The above composition, wherein the component (c) is selected from the group consisting of dicyandiamide, diphenyl diamino sulfone, novolac resin, melamine phenol novolac Resin, one of or a combination of a benzoxazine resin, a bisphenol A/F type benzopyrene resin, a poly/phenylene polyphenylene oxide. The above composition, wherein the component (D) is selected from the group consisting of ceria, aluminum nitride, aluminum hydroxide, aluminum borate, magnesium hydroxide, boron nitride, calcium carbonate, Φ talc, zinc sulphate, clay , one of trioxide, titanium dioxide glass powder, mica powder or a combination thereof. The above composition wherein the (D) component has a particle diameter of 0.1 to 20 μm. In the above composition, the amount of the component (D) to be added is from 〇 to 75% by weight, preferably from 20 to 60% by weight, based on the total mass of the compositions (A), (Β) and (C). The above composition wherein the (Β) component is contained in an amount of 5 to 50% by weight, preferably 1 to 5 to 35% by weight, most preferably 5 to 25% by weight. The above composition wherein the content of the component (C) is 2 to 70% by weight, preferably 5 to 60% by weight, most preferably 1 to 45% by weight. The use of the above composition is for the manufacture of a prepreg, a metal laminate, a printed circuit board, a coated material or a semiconductor package carrier. Therefore, the halogen-free flame-retardant resin composition of the present invention has good flame retardant properties by using a specific phosphorus-containing phenol-based resin hardener, and has high dimensional stability and low hygroscopicity; Epoxy resin and chain extender, with other excellent characteristics, such as good electrical characteristics, low energy 201136982 coefficient of dispersion; good plus good heat dissipation characteristics, work characteristics, suitable for punchable process; suitable for heat dissipation substrate . θ In addition, the present invention can produce the following various unpredictables by transferring the flame-retardant or nitrogen atom mainly by transferring the per-oxygen resin of 4 to the resin hardener or bond extender of the disk. Efficacy: (1) Since the % oxygen resin can be used without filling, its glass transition temperature is suitable for 2's lack. For example, any epoxy resin with ordinary or high glass transition temperature can be used; = A wide range of epoxy resins can be used, so it is possible to improve the characteristics of the formed substrate by using a special type of epoxy resin. For example, manufacturing a substrate that is used in a press process; Shake: a wide range of epoxy resins can be used. The use of a filling agent can also be applied to the chain extender, and the user can select a specific type of chain extender (the electrical characteristics of the formed substrate, such as reducing the dielectric loss. </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; • In this component: the temple is restricted to 'the use of the moon can be used for a better example'. ^ Lacquer type epoxy resin, tetra-functional (four) type resin, coffee base resin, phosphorus-containing epoxy Resin, 201136982 can be used alone or in combination of two or more. The so-called secret varnish type epoxy resin refers to the compound of the ship varnish type structure, for example: surface type epoxy tree: epoxy resin, naphthalene _ Epoxy Resin and Shuangyi The so-called double-check epoxy resin refers to a compound having a double structure in the molecule, for example, a double-layer A epoxy resin and a double-fence epoxy resin.

The so-called phosphorus-containing epoxy resin can be reacted with any epoxy resin disk organic ring (tetra) compound (HCA) to obtain a side bond containing a Wei oxygen resin, for example, a double A epoxide _, an object F epoxy resin, a secret Secret type epoxy resin, nail powder type epoxy resin, naphthalene (10) _ epoxy resin, double A phenolic epoxy resin, etc. - side chain phosphorus ring obtained by reaction with organic cyclic phosphide (hca) Oxygen resin. The tetrafunctional epoxy resin thereof is, for example, 1,1,2,2-tetra(p-phenylphenyl)ethane tetraglycidyl ether, N,N,N,,N,-diaminodiphenyl Methane tetraglycidyl ether. In the halogen-free flame-retardant resin composition of the present invention, the chain extender of the component (C) is not particularly limited, and a chain extender for a laminate may be used, and preferably includes, but is not limited to, dicyandiamide. Dixiandiamide, diphenyl diamino sulfone, novolac resin, melamine phenol novolac resin, benzoxazine resin, bisphenol A/F type benzopyrene resin, polyphenylene oxide 〇 In the halogen-free flame-retardant resin composition of the present invention, the inorganic 201136982 filler powder of the component (D) is not (4) Limitations, f can be used for the inorganic filler powder for the laminate, preferably exemplified but mixed: dioxane, nitriding, chlorination, side acid, magnesium hydroxide, nitriding, carbonic acid Office, talcum powder, boric acid, clay, alumina, titanium dioxide glass powder, mica powder. In the dentate-free flame retardant resin composition of the present invention, the scaly phenol resin hardener of the component (B) is a compound of the following formula (1): a compound of the formula (1):

Wherein n and m are both deuterium or 1, and when it is deuterium, it represents that the bond to the chemical bond is hydrogen; Ri is hydrogen or an alkyl group; and HCA is a compound of the following formula (2): a compound of formula (2):

0 = ΖΡ-0 2 , wherein R2 is a substituted or unsubstituted alkylene group of 0 to 5 carbons. The phosphorus-containing phenolic resin curing agent of the component (B) can be obtained, for example, by reacting a bisphenol A phenol resin or a bisphenol F phenol resin with HCA. Further, in this case, in the preferred case, the phosphorus-containing phenolic resin hardener of the component (B) may be physically added or chemically incorporated into a specific inorganic component, such as Shi Xi, and the ratio may be 0.1 to 3%. The varnish prepared by using the halogen-free resin composition of the present invention may be impregnated with a suitable substrate, and after the substrate is dried by heating, a prepreg may be obtained and a plurality of prepreg bodies may be stacked. Made into a laminate. Wherein, examples of the foregoing substrate include, but are not limited to, a fibrous substrate such as glass fiber, metal fiber, carbon fiber, aromatic polyamide fiber, pB fiber, LCP fiber, Kevlar fiber, cellulose, etc.; fiber mat (Mat Substrates, such as fiberglass; and paper substrates, such as aromatic silk fibroin paper, (10) paper, and Kevlar paper. The prepreg body of the temple may be combined with a piece or a plurality of pieces, and placed on the upper side of the =1 surface, and the composite material laminated board obtained by the step of preparing the composite material under the pressure heating condition An electric crying paint such as sex, heat resistance, hygroscopicity, and electrical properties. , Taigong, Father Pass, "Speed Board." Σσ, as used in the manufacture of printed circuit boards and multilayer circuits.

X~U / . Through the example of the actual addition of each component (in solid content), after reading the laminate, read her composition, and: fat hardener, as the real two: Example: no added (10) Rut. The ingredients of 201136982 in the examples and the comparative examples are as follows: Epoxy resin 1 is a varnish epoxy resin with an epoxy equivalent of 195 to 215 g/eq. Epoxy 2 is a di-glycidyl ether of A, with an epoxy equivalent of between 180 and 200 g/eq. The can-containing epoxy resin 1 is a side chain phosphorus-containing epoxy resin obtained by reacting a acetal epoxy resin with an organic cyclic phosphide (e.g., HCA), and has an epoxy equivalent of from 330 to 360 g/eq. The epoxy resin containing 2 is a side chain phosphorus-containing epoxy resin obtained by reacting an acid epoxy resin with an organic cyclic filler such as HCA, and the epoxy equivalent is from 300 to 330 g/eq. The epoxy resin containing 3 is a side chain phosphorus-containing epoxy resin obtained by reacting a double epoxy resin with an organic cyclic filler (such as HCA-HQ), and the epoxy equivalent is between 310 and 360 g/eq. . Chain extender 1 represents dicyandiamide. The chain extender 2 represents a phenolic resin having an active hydrogen equivalent of from 4 to 108 g/eq. Chain extender 3 represents melamine phenol novolac resin produced by DIC Corporation. The nitrogen content is about 8 to 19 percent. The chain extender 4 represents a bisphenol F type benz® xazine resin having a nitrogen content of about 5 to 8 percent. Chain extender 5 represents a bifunctional polyphenylene ether resin (PPO resin) produced by SABIC Corporation having a molecular weight of about 1700 to 2000 g/eq. The hardening accelerator represents 2-methylimidazole (2MI). 12 201136982 Phosphorus-containing resin hardener represents the phosphorus-containing resin (PPN resin) produced by SHIN-A T&amp;C, with a phosphorus content of about 9.4%. Table I:

Example----'~-1 Comparative Example Item 1 2 3 4 5 6 --------- 7 Epoxy Resin 1 (g) 100 100 100 100 100 140 ----Epoxy Resin 2(g) 58 20 5.3 Phosphorus-containing epoxy resin 1(g) ---- 100 Phosphorus-containing epoxy resin 2(g) 26 24 24 Phosphorus-containing epoxy resin 3(g) 6 Chain extender 1(g) 0.30 0.38 4.0 3.2 bond extender 2 (g) 32 32 &quot; . bond extender 3 (g) 12 24 28 '- - chain extender 4 (g) 12 21 chain extender 5 (g) 100 ---- -- Hardening accelerator (g) 0.12 0.15 0.12 0.12 0.12 0.42 0.14 Phosphorus phenolic resin hardener (g) 36 52 34 34 42 62 Inorganic filler powder (Si〇2 and ATH* &gt; 1:1) 30% 30 % 30% 30% 30% 30% Inorganic filler powder (Si02) 15% Note*: Aluminium trihydrate (ATH) The resin varnish blended with the above composition is impregnated with glass fiber cloth and dried at 170 ° C. After drying to a pre-impregnated body under conditions, eight sheets of pre-impregnated bodies were laminated, and a piece of 35 um copper foil was placed thereon, and pressed at 190 ° C and 25 kg / cm 2 to form a composite laminate. The obtained laminates are tested for glass transition temperature according to International Printed Circuits Association test standard IPC-TM-650 2.4.25; IPC-TM-650 2.5.4.4 tested dielectric constant and dissipation coefficient; according to iPc_TM-650 2.4.24.1 13 201136982 Test T288 and T300; test cracking temperature according to IPC-TM-650 2.4.24.6; test solder resistance according to IPC-TM-650 2.4.13.1; burn test according to 1 4-1\4-650 2.3.10. The test results are shown in Table 2: Table 2

EXAMPLES Comparative Example Item 1 2 3 4 5 6 7 DSC-Tg (°C) 165 135 175 195 185 180 155 Cracking temperature (5 wt% loss) &gt; 360 〇 C &gt; 360 〇 C &gt; 360 〇 C &gt; 360〇C &gt;360〇C &gt;350〇C 350〇C solder resistance (288°C) &gt;300s &gt;300s &gt;300s &gt;300s &gt;300s &gt;300s &gt;180s high pressure moisture absorption (1 atm , 24hr) ~1.00% ~1.00% ~1.0()% ~1.00% ~1.00% ~1.00% -1.50% Γ288 &gt;30min &gt;30min &gt;60min &gt;60min &gt;5min &gt;10min ~l.Omin T300 &gt;5min &gt;5min Dielectric coefficient (1G) 4.7 4.7 4.7 4.7 4.7 4.2 4.7 Escape coefficient (1G) 0.015 0.015 0.015 0.015 0.015 0.012 0.015 Combustion test 94-VO 94-VO 94-VO 94-VO 94-VO 94 -VO 94-VO It can be found from Table 2 that the non-volatile flame-retardant resin composition of the present invention has better flame retardant properties and is more resistant than Comparative Example 7 in which the phosphorus-containing phenolic resin hardener is not added. Dimensional stability, low moisture absorption; with appropriate epoxy resin and chain extender, it has other excellent characteristics, such as good electrical characteristics, low dissipation coefficient; good processing characteristics, suitable for rushing Bed process. As described above, the present invention fully complies with the three requirements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the present invention is applied to a fang-free flame-retardant resin composition by using a specific (4) secret resin hardener, so that it has good flame retardant properties, and has a high stability of 201136982 size. , low moisture absorption; with the appropriate epoxy resin and chain extender, to improve the electrical and processing characteristics of printed circuit boards; in terms of industrial availability, the use of the present invention Products, when fully meet the needs of the current market. The invention has been described above in terms of the preferred embodiments thereof, and it is understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations that are equivalent to the embodiments are intended to be within the scope of the present invention. Therefore, the scope of protection of the present invention is defined as the following in the scope of the patent application below. [Simplified illustration] jttk 〇 [Description of main component symbols]

Claims (1)

201136982 VII. Patent application scope: 1. A halogen-free flame-retardant resin composition comprising: (A) an epoxy resin; (B) a phosphorus-containing phenolic resin hardener; and (C) a chain extender. 2. The composition of claim 1, which may further comprise (D) an inorganic filler. 3. The composition according to claim 1 or 2, wherein the (B) compound is a compound of the following formula (1) or a modified substance thereof, the compound of the formula (1): Wherein n and m are both 0 or 1; h is hydrogen or an alkyl group; HCA is a compound of the following formula (2), a compound of the formula (2): 0 = P-0 wherein R2 is a substituted or unsubstituted alkylene group of 0 to 5 carbons. 16 201136982 4. The composition of claim 3, wherein the component 1 of the component (B) is 700 to 2200 g/mol, the filling content is 5 to 12%, or the selectivity is physically or chemically. Add 〇.1~3%. 5. The composition of claim 1 or 2, wherein the component (A) is selected from the group consisting of a bisphenol type epoxy resin, a novolak type epoxy resin, a tetrafunctional bad emulsion resin, and a ring-containing ring. Oxygen resin or a combination thereof. 6. The composition of claim 1 or 2, wherein the component (C) is selected from the group consisting of dicyandiamide, diphenyl diamino sulfone, and nicotac Resin), melamine phenol novolac resin, benzoxazine resin, biguanide A/F benzopyrene resin, polyphenylene oxide Or a combination thereof. 7. The composition of claim 2, wherein the component (D) is selected from the group consisting of silica dioxide, aluminum nitride, aluminum hydroxide, aluminum borate, magnesium hydroxide, boron nitride, calcium carbonate. , talc, zinc borate, clay, aluminum oxide, titanium dioxide glass powder, mica powder or a combination thereof. 8. The composition according to claim 2, wherein the component (D) has a particle diameter of 0.1 to 20 μm. 9. The composition of claim 2, wherein the amount of the component (D) is greater than 〇% by weight based on the total weight of the components (A), (Β) and (C) Less than or equal to 75% by weight. 10. The composition according to claim 9 of the invention, wherein the amount of the component (D) is 20 to 60% by weight based on the total weight of the components (A), (Β) and (C) . The composition according to claim 1, wherein the component (B) is 5 to 50% by weight, and the component (C) is 2 to 70% by weight. 12. The composition according to claim 11, wherein the component (B) is contained in an amount of 5 to 35% by weight, and the component (C) is contained in an amount of 5 to 60% by weight. 13. The composition according to claim 12, wherein the component (B) is contained in an amount of 5 to 25% by weight, and the component (C) is contained in an amount of 10 to 45% by weight. A phosphorus-containing phenolic resin hardener which is a compound of the following formula (1) or a modified form thereof, a compound of the formula (1): Wherein n and m are both 0 or 1; I is hydrogen or an alkyl group; HCA is a compound of the following formula (2), a compound of the formula (2): 0 = P-0 wherein R2 is a substituted or unsubstituted alkylene group of 0 to 5 carbons. 15. The hardener according to claim 14, wherein the molecular weight is 18 201136982 700 to 2200 g/mo, the phosphorus content is 5 to 12%, or the inorganic or chemically added 0.1 to 3% inorganic ingredient. 16. Use of a composition according to any one of claims 1 to 13 for the manufacture of a prepreg, a metal laminate, a printed circuit board, a coated material or a semiconductor package carrier . 201136982 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: