TW200817469A - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition is provided. The composition comprises an epoxy resin component, a fire retardant component, and a curing agent component. The epoxy resin component is selected from the group consisting of a bisphenol A type epoxy resin, a novolac type epoxy resins, and a combination thereof. The fire retardant component is selected from the group consisting of a phosphorus-based fire retardant, a hydrophilically processed inorganic metal hydroxide, and a combination thereof. The curing agent component comprises a dicyandiamide compound and a low temperature catalyst. The fire retardant component is used in an amount ranging from 50 to 200 parts by weight based on 100 parts by weight of the epoxy resin component, and the curing agent component is used in an amount ranging from 1 to 20 parts by weight based on 100 parts by weight of the epoxy resin component.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, and more particularly to a halogen-free flame retardant thermosetting resin composition. [Prior Art] As is known to those skilled in the art, basic materials of flexible printed drcuit boards include copper foil substrates, cover films (i.e., protective films), and other components. Among them, the copper foil substrate generally comprises a copper foil, a substrate, and an adhesive as a medium, and the cover film comprises two parts of an adhesive and a substrate. Here, since the flexible printed circuit board is used in a higher temperature environment, the adhesive used for the copper foil substrate or the cover film needs to have a certain degree of flame retardancy and reliability. Epoxy/butadiene rubber (Ep〇xy/NBR) systems are commonly used in this application. Since the ignition point of the epoxy resin is not enough to load the high temperature of the circuit environment, in addition to the resin/rubber component, the addition of the flame retardant to the electronic material is required to pass the UL_94 fire test V_〇. For example, the tooth-containing compound of jetrabromobisphenol A (TBBA) is a common flame retardant for improving the flame retardancy of the ring resin. However, when such a halogenated flame retardant such as tetrabromide diol is burned at an inappropriate temperature, toxic substances such as dioxin or benz〇fbran may be produced, which may endanger human health and cause environmental pollution. In addition, although the above epoxy resin/butadiene rubber system can meet the requirements of flame retardant properties, since the interface is a glossy copper surface, there is still a lack of subsequent properties, which cannot meet the requirements of tear resistance and weather resistance. Herein, a dicyandiamide hardener is generally added to promote adhesion to the shiny copper surface. This 5 200817469 uses '^ to improve the adhesion between the adhesive and the shiny copper surface, but the crystal is made to make the formed material highly hygroscopic. In addition to the problem of blasting, the high-resistance is more likely to cause metal between the lines. _^=Restriction of Hazard〇us 齿" The tooth material is gradually replaced by an unmaterial material. In order to meet the requirements of the beach, the use of materials, ratios and processes are more difficult to achieve. Knowing that today's soft printed circuit board materials are used to affect human health and cause environmental burdens, etc. 4fAt eight improved the elimination of the existing soft printed circuit board material ϊϊ ϊϊ 印刷 印刷 印刷 、 、 、 、 、 、 、 、 、 、 、 、 、 、 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 It can be used as a MU:k plate as an adhesive. The composition comprises an epoxy resin component, f Α surface oxygen resin, Lai resin, and a combination thereof; it is difficult to be selected from the following groups. Burning agent, low affinity inorganic gold, and combinations thereof; hardened thief (4) containing - dicyandiamide compound and a part of Γο 5 ΪΛ ° I flame retardant component content per 100 parts of epoxy resin component Heavy' and hardener component content per 100 Heavy epoxy resin into 6 200817469 parts 1 to 20 parts by weight. Another purpose of A month is to provide a thermosetting resin composition which can be used as a protective film for the brakes 2 = road board. The composition comprises - epoxy resin Into: miscellaneous factory, sub- and: hardener composition. Shot, epoxy resin component selection ship 1 Ί: also look for A-type epoxy resin, _ epoxy resin, and the combination of the above; from r group: phosphorus-based flame retardant The agent, the affinity-treated inorganic-f-dimer-U combination, the hardener component comprises a dicyandiamide compound and a Cao Wen type catalyst, wherein the content of the flame retardant component is per touch.

It is 5G to part by weight, and the content of the hardener component is 1 to 20 parts by weight per 100 parts by weight of the latex component. Another object of W is to provide a thermosetting resin composition which can be used as an adhesive film for a circuit board. The combination of the J bis bisphenol quinone type oxy-resin, the phenolic epoxy resin, and the aforementioned group I machine are selected from the group consisting of a dish-based flame retardant and an affinity treatment.

U : ίίί = Γ and combinations thereof; the hardener component comprises a dicyandiamide compound, a low temperature catalyst of Lewis acid. = the amount = 5G to heavy epoxy resin per touch

The thermosetting resin composition having a content of the epoxy resin component per gram of epoxy resin to 2 Gf^$ and having a better J has good material-adhesive properties, difficulty in handling, and weather resistance, and the material forest is contained in an environment-dependent environment. Green material H, after the implementation of the embodiment described by iinii, the technical field has the general purpose of ======== and Wei (four) purposes, - the present invention 7 200817469 embodiment] the sputum hair complex can be used for soft printing The circuit board is provided to provide a viscous composition comprising an epoxy resin component, a flame retardant component, and an epoxy resin suitable for use in the composition of the present invention. (4) A (bisphend Α二自^The lower group (but the resin is 15 〇 to medium 5 and the bisphenol A type epoxy 2000 goes to H" and the weight average molecular weight is 300 to the structure size, and the double-layer AM epoxy resin can further distinguish f乂 and short-chain two-year-old type A (four) is _ ring _ purpose. Among them _; bond and A type epoxy resin average molecular weight is long epoxy tree I intended to quiet molecule 4 is 6m = fine 1 chain bisphenol a lipid The average molecular weight is 300 5 6 nn, and the chain bisphenol A type epoxy tree-〇-500^^t::; l^ t 〇社 a Any suitable fineness of the foregoing epoxy resin used in the composition of the present invention is a combination of two or more epoxy resins to provide the second embodiment of the present invention. Limit to this) ^ ^ Ring A _ Oxygen_ _ _ mixture or ' * Oxygen resin without _ lipid resin mixture, as the hair of the Wei = bismuth epoxy resin composition. & month, and δ The flame retardant component suitable for use in the composition of the present invention is selected from the group consisting of inorganic metal hydroxides treated with S! parental ion, and combinations thereof: 3 series" is used per 100 parts by weight of epoxy resin component. 5 = ', preferably 50 to 1 part by weight per 100 parts by weight of the epoxy resin component. This portion 8 200817469 When a combination of a phosphorus-based flame retardant and an affinity-treated inorganic metal hydroxide is used When it is a flame retardant component of the present invention, it is preferred to use a mixture of a scale-based flame retardant and an affinity-free metal-free hydroxide in a weight ratio of 2:1 to 1:2. A solvent-based phosphorus-based flame retardant can be used in the present invention, and can be used in the present invention without affecting the processing characteristics of the material. Phosphorus-based flame retardants include (but not limited to) PX200, PSB100, trimethyl phosphate, diethyl phosphate (tetra) ph〇sphate TEp), tributyl phosphate ( Tril^yle phosphate), triphenyi ph〇Sphate Tpp, 曱

U $ dimethyl methyl phosphate (DMMP), triphenyl phosphate, trimethylphenol phosphate (tricresyi 〇 __, ^ 曱 曱 曱 磷酸 曱 tri tri tri tri tri Cre phenol phenyl phosphate (cres^ Phenyl phosphate), cresyl double 2,6-dimethylphenyl phosphate ((such as di 2'6 xylenyl phosphate), diphenyl-2-vinyl styrene Diphenyl-2-metacryl〇yl〇xyethyl phosphate, aromatic condensed phosphate, etc. Suitable for the affinity treatment of inorganic metal hydroxides as a flame retardant component of the present invention, the surface is covered with Inorganic metal hydroxide particles of silane. Among them, unsubstituted or substituted decane may be used in this application. For example (but not limited thereto), triethylchloromethane (triethylchl may be used).石r〇silane), diunethyldichlorsilane, etc., which are provided on the surface of the inorganic metal hydroxide particles to provide the flame retardant component. Examples of inorganic metal hydroxides (but not limited to this)··· A magnesium oxide, aluminum hydroxide magnesium carbonate hydrate, nickel hydroxide, barium titanium oxide, barium hydroxide, etc., may also be a combination of the above hydroxides. The hardened ship contains - a dicyandiamide compound and a low-thickness type agent, and the content is 2 to 2 parts by weight per part by weight of the epoxy resin, preferably 100 parts by weight of the epoxy resin. The composition is 4 to 1 part by weight. In addition, the content ratio of the double-amine amine compound 9 200817469 to the low-temperature catalyst in the hardener component is 1:1 to 1〇: 丨, >^4:116:1. The dicyandiamide compound includes dicyandiamide and dicyandiamide adducts. The so-called "low-temperature catalyst" is based on the low temperature of the carmaker (that is, lower than the initial curing temperature of the epoxy resin).丨5〇 about it) 'such as: a catalyst for accelerating the hardening reaction of epoxy resin between 130 and 15 (hardening temperature between TC). Different low temperature type catalysts may be selected for the composition of the present invention as needed. For example, Optional low temperature catalyst package (but not this): Miqua-type low-temperature catalyst and Lewis acid low-temperature catalyst. Specifically, if an imidazole-based low-temperature catalyst is used in the composition of the present invention, in addition to providing the subsequent performance, The layer of material formed can also be used directly as a cover film for protecting printed circuit boards. Here, the substituent on the imidazole is also not subject to any limitation. For example, imidazoles may be used, but not limited to, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-indole 2-ethyl-4-methylimidazole, 1-benzyl-2-ylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 _ Cyanoethyl 2_ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, And 2-phenyl-4-mercapto group via 2-phenyl-4-methyl-5-hydroxymethylimidazole. Further, if a Lewis acid is used as the low-temperature catalyst in the composition of the present invention, the material layer provided has particularly good adhesive properties. Any suitable Lewis acid type low temperature catalyst can be employed in the compositions of the present invention. Preferably, a borofluoride is used in the composition of the present invention, for example (but not limited thereto) boron trifluoride monoethylamine complex (BF3. MEA) And diethanolamine difluoride (b〇r〇n trifluoride triethylamine, BF3. 200817469

Et3N) 另 An aromatic amine compound may be further contained in the hardener component as needed. By way of example and not limitation, the following aromatic amines may be employed: diaminodiphenyl methane (DDM), such as 3,3-diaminobiphenyl wind (3,3) '-diaminodiphenyl sulfone, 3,3'-DDS) and 4,4'-diaminodiphenyl sulfone (4,4'-DDS) diaminodiphenyl sulfone (diaminodiphenyl sulfone) DDS), such as 4,4'-diaminodiphenyl ketone (4,4, _diaminobenzophenone, 4,4'-DBP) diaminobenzophenone (DBP), 3,3, 5,5,-Tetramethyl-4,4,diaminobiphenylene (3,3,5,5,-tetramethyl-4,4,-diaminodiphenyl sulfone, TMDS), and combinations thereof. The content of the aromatic amine compound in the hardener component may be from 〇 to 7 〇 by weight.组合 The compositions of the present invention can be used in a conventional manner. For example, an inorganic filler such as aluminum hydroxide or magnesium hydroxide may be first dispersed in a benzene solvent and treated as a dispersion under ball milling. An elastomer such as butadiene (bn) rubber and a flame-retardant woven fabric are added to the dispersion, and the mixture is mixed at a high speed or reduced to a certain extent. After the beans, a solution such as a ketone (e.g., methy ethylketone) is dissolved as a solution of the milk resin component and mixed with a cake. Further, the hardener component and the low-temperature catalyst are dissolved in, for example, 2-ethyl ethyl cellulose, and the mixture is stirred and dissolved to obtain another solution. The above two solutions

St-100-coating sticks make the sickle or roll (four) dissolve on the paste. The paste is baked in an electric heating oven at 1 °C to just after. The temperature of C is baked 5 77 until it is in a semi-hardened state (B-s_. Thereafter, it is bonded to the release paper by a roller type 200817469 laminating machine, and then the temperature is 50 to 8 (the hot plate of rc is bonded) , then ^ is preheated for 0 to 5 seconds, molding for 60 to 120 seconds, hot pressing temperature is 16 〇 to 190 °C pressure 75 to 12 〇 Kg / cm 2, hardening temperature range between 150 and 190 ° C, hardening time 1 to 3 hours, the material is formed. Here, if the carrier film is a non-release type polyamide (PI) film, the laminated product is a protective layer which can be used as a cover film, and if the surface is away from the surface The polyethylene terephthalate (pET) film can be applied as an adhesive layer. The following specific embodiments are used to further illustrate the present invention. As follows: (1) Peel Strength test: According to the IPC TM 65〇2 4 9 method, a test piece of 1 cm width is cut out, and then the strength is tested by a tensile machine. (2) Solder-ability Test: According to the method of pPC TM 65〇2 413, the test piece is placed in a high temperature environment (such as a soldering furnace) for a period of time. Observe the change. (3) Anti-Chemicals test: Test and test according to IPC TM 65〇2 3 2 method. (4) (3) (6) (7) Effluent or Resin Flow test : According to the ipc tm 650 2.3 17 method, make a test piece and test it. UL-94 certified V_ flammability test ~, y piece, and use flame retardant test machine for flame-retardant test. (Surface Resistance) test: According to the jpc 650 650 2.5 17 method, make a test piece, and use a high-impedance machine for surface impedance test: · Weather resistance test · · Place the test piece on a constant temperature mosquito and constant, crystal 85 In the environment of %RH, the characteristics such as the strength and heat resistance of the test piece are measured': Several embodiments of the present invention are as shown in the following table, and examples -

The use of the inventive composition on the side of the protective layer is five and six. Regarding the use of the composition of the present invention in an adhesive. J 12 200817469 In pi, the solution obtained by the above preparation is coated with a polyimide film suitable for 12.5 micrometers (or polyethylene phthalate cloth is dried and the film thickness is 2 〇 micrometers). After bonding, protect the H) layer. (4) Relying on changing the epoxy resin in the epoxy resin component to dicyandiamide compound (for the production of AjIN〇M〇T〇) = AH15 4 dicyandiamide adduct D or Dicyandiamide D2) and aromatic amines = added amount. P5 and P6 are available with different hardeners. Among them, p5 uses dicyandiamide (D2) and dicyandiamide adduct (D1) as hardeners; P6 hardener is another embodiment of D1 and D2 content and using different catalysts. ... 200817469

2 73.25 10.25 16.30 45.35 40.69 ΜΕΚ j 1 5.2326(D2) 1.0901 1.50 Toughness is not the same 0.164 1.103Ad/Ad 288 or more 0.265 V-0 1.23 0.72 0.36 0.59 m CU 73.25 10.25 16.30 45.35 40.69 ΜΕΚ 6.1541 1.9099 (D1 1.0610 1.46 OK Tough The same 0.132 1.123Ad/Ad 288 or more 0.179 V-0 1.12 0.89 0.73 0.68 CN PU 73.25 10.25 16.30 45.35 40.69 ΜΕΚ 6.7587 3.5145(D1) 0.4055 ! 1.86 o Toughness is not the same 0.144 1.052Ad/Ad 288 or more 0.214 V-0 1.05 0.88 0.92 0.79 TH Dh 73.25 10.45 1 16.30 45.35 40.69 ΜΕΚ j 1 9.5581(D1) 1.9913 2.74 o Toughness is not different 0.179 0.625Cu/Ad 〇〇〇〇(N 0.179 V-0 1.12 0.450 0.431 0.382 Experiment No. δ Hydroxide Minghao 200 Solvent DDS D1 or D2 Catalyst A/C (Weight Ratio) Three Rollers Coating B-stage Film State Press Fit Appearance (mm) Next Strength (Kgf/αη) Heat Resistance (°c) MEK (mm) Flame retardant 1 120hr 240hr 500hr epoxy phenolic resin flame retardant 3 hardener physical properties chemical properties weatherability (85〇C, 85RH%) < U B-stage C-stage inch one 200 817469 :/ c

Oh 73.25 10.25 16.30 40.69 IPA/MEK 3.5145 9.5581 1.9913 (imidazole) MEK/DMF 1·50 PET-L (36) in (N 130 X 3.0 Tough no different 0.263 2.907 Ad/Ad 288 0.148 2.77 2.22 PET-L (36) 6 to i 130 X 2.5 Tough and no different 0.170 2.940 Ad/Ad 288 0.148 2.84 2.53 in Cu, 73.25 10.25 1 16.30 40.69 IPA4/MEK 9.5581 2.3895 1.9913 (Louis acid) MEK/DMF5 2.74 PET-E (36) (N 130 X 3.0 Toughness is not the same 0.274 1_ 2.990 Ad/Ad 288 0.157 2.92 2.62 PET-E (36)5 rH 130 X 2.5 Tough and no different 0.185 3.107 Ad/Ad 288 0.155 3.09 2.74 Implementation No. 00 PX200 Solvent Ή Q <NQ Catalyst Solvent A/C f Thunder Ratio) Release Film (μm) Adhesive Thickness (μm) Dry (.CXmin) B-stage Film Conditioned Appearance (PI/Ad/PI) Ejection (mm) Next Strength (Kgf /cm) Heat resistance (°C) 1 120hr Next strength (Kgf/cm) Bis A Hardener < U Three-roller coating Physical properties Chemical properties Weatherability (85〇C, 85RH%) Coating conditions B-stage C- Stage Η撇lol 200817469 言主····· L: long-chain bisphenol A epoxy resin. 2· Μ ··· Phenol a type epoxy resin 3· S ··Short chain bisphenol a type epoxy resin 4· IPA ··Isopropanol (〇propanol) 〇5· PE1VE •• is a J.Lin enterprise limited The company's product PET-200 film. 6· PET L is a product of Linyi Yuke Co., Ltd. 1 plus (3) plus 丨 (10)) PET-38AL-5 film. 7. DMF • Dimethyl ethaneamine (dimethyl fb_mide). Moreover, it can be seen that the composition of the present invention contains no material of the material provided by the halogen. It also has good flame retardancy and weather resistance, and can eliminate the problems caused by the materials used in the printed circuit board. The examples of the invention are exemplified to illustrate the embodiments of the present invention and to explain the present invention. Any scope of the rights of the invention that is familiar with this technology should be based on the scope of the patent application.

Claims (1)

200817469 X. Patent application scope: 1. A thermosetting resin composition comprising: A ^ The following group: filling a flame retardant, affinity, a combination, and combinations thereof; as well as In beans, 丨1, 'contains a double amine compound and a low-temperature catalyst' i 200 = the content of the tongue component is 50 parts per 100 parts by weight of the epoxy resin component 1 i 2 〇 'fii hardener component The thermosetting resin composition according to Item 1, wherein the hardener component is contained in an amount of from 4 to 10 parts by weight based on 100 parts by weight of the epoxy resin component. The thermosetting resin composition according to Item 1, wherein the flame retardant component is contained in an amount of from 50 to 100 parts by weight based on 100 parts by weight of the epoxy resin component. 4. The thermosetting resin composition according to the above, wherein the double-type epoxy resin epoxy has a range of 150 to 1000, and the epoxy equivalent of the resin is 5·=request, 4 The thermosetting resin composition, wherein the bisphenol A type epoxy resin has a weight average molecular weight ranging from 300 to 2,000. 6. The thermosetting resin composition according to claim 5, wherein the resin component is a bisphenol A oxyresin, and comprises a long-chain bisphenol A type epoxy resin, a medium chain bisphenol A type epoxy resin, and/or Short-chain bisphenol A epoxy resin. 7. The thermosetting resin composition according to claim 1, wherein the disc-based flame retardant and the 200817469 affinity-treated inorganic metal hydroxide have a weight ratio of 2: i to i: 2. Soluble in the heat of the composition, the towel, the heat-resistant resin composition, and the flame retardant package 11. The tumbling fat composition of claim 1 wherein the metal hydroxide is aluminum hydroxide. 12. The thermosetting resin composition according to Item 1, wherein the dicyandiamide compound is dicyandiamide. The thermosetting resin composition according to claim 1, wherein the dicyandiamide compound is an adduct of dicyandiamide. The thermosetting resin composition according to claim 1, wherein the low temperature type catalyst is an imidazole. The thermosetting resin composition according to claim 1, wherein the low temperature type catalyst is a Lewis acid. The thermosetting resin composition according to claim 3, wherein the weight ratio of the dicyandiamide compound to the low-temperature catalyst is from 1:1 to 10:1. The thermosetting resin composition according to claim 1, wherein the weight ratio of the diamine compound to the low temperature catalyst is from 4:1 to 6:1. The composition of claim 1, wherein the hardener component further comprises an aromatic amine: the thermosetting resin composition according to Item 18, wherein the aromatic amine compound k is from the group below · 3,3-diaminobiphenyl sulfone, 3,3'-DDS), 4, decylaminodiphenyl sulfone (44, _diamin〇diphe s^e, 4,4'-DDS), 4 ,4,_Diaminobenzophenone-diaminobenzophenone, 4,4, DBP), 3,3,5,5,-tetramethyl-4,4,-diaminodiphenyl sulfone (3,3,5 , 5, *amethyi_4, 4, _diamin〇diph isuif〇ne TMDS), and combinations thereof. The thermosetting resin composition of claim 14, which is for providing a protective layer. A thermosetting resin composition as claimed in claim 15 which is for providing an release layer. +100. The thermosetting resin composition according to claim 1 is used for a flexible printed circuit board. 0 200817469 VII. Designation of representative drawings: (1) The representative representative of the case is: None. (2) Simple description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: