TW574262B - Imide based oligomer having acid anhydride at terminal, and resin composition having curing property - Google Patents

Description

State of the Invention (Field of the Invention This month is Guanwan; an epoxy oligomer having an imidyl group at the end, with G " and I imine oligomers as epoxy hardener epoxy: Fat composition. More specifically, the present invention relates to a kind of fluorene imide oligo which has excellent mutual solubility with epoxy resin, so it does not need to be used substantially, and 4 red is suitable for use as an epoxy resin hardener. The invention relates to a variety of hardenable peroxy resin compositions, which can produce hardened materials with low stress including low breaking stress and low bending elastic modulus. BACKGROUND OF THE INVENTION In recent years, '-pole camp, two dozen ^ τ ^ two poles g, le, LSI and other semiconductor devices are sealed by a thermosetting resin. Among them, epoxy resins are generally used because they can achieve a balance in performance. Second, 1 = device installation will move toward surface mounting. In the semiconductor device, the Ting tin immersion method immersed directly in the solder bath is used. At this time, the temperature will become higher, the entire crystal; the heart rate xe will cause a great stress', which will cause cracks in the seal. With == in sealed Oxygen resin, the problem of oxygen resin when it becomes a hardened material. 'Related research has divided butadiene gum and genus into epoxy resin composition, or introduced oxygen-based groups into epoxy resin molecules, or Various suggestions such as this hardener molecule. Beep in = Yes: etc. Suggestions 'Its dispersibility and miscibility are extremely poor ..., a hardened product with a heterogeneous phase separation structure' is therefore very difficult: This paper is of suitable size Caiguo -4- 297 mm) 574262 A7 ------------ ---_ B7 V. Description of the invention (2) "-Give sufficient low stress. In addition, in terms of using the sealing material as a single-liquid type with fluidity, since the material will bond and collect fat (chppmg) at relatively low temperatures such as Dang, ® ^ ^ • • This temple uses this penetration Semiconductors and diodes are sealed, etc .; When using this method, liquid epoxy resins and semi-solid open / or hard coat varnish hardeners or liquid acids, "A, amine, etc." A kind of sealing material using semi-solid or solid self-requested varnish hardener is not only poor / lodged; if a solvent is used, the solvent b is absorbed in the soil & sealing material after hardening. , Will have an adverse effect on its performance. If they use ordinary acid anhydride, amine, and ammonium-based hardeners to form a non- / d-type secondary sealing material, they will not be able to obtain a uniform curable resin composition, or they will cause a problem of low reliability. point. In order to solve these problems, it is gradually necessary to find a hardener which has fluidity and mutual growth and the hardened material exhibits low stress. SUMMARY OF THE INVENTION An object of the present invention is to provide a hardener which can produce a solvent-free hardening resin composition, has fluidity and mutual solubility, and has a hardened hardened body with low stress. In addition, another object of the present invention is to provide a curable resin composition which is a non-solvent type 'and that the cured product has low stress. That is, the present invention relates to a fluorene imide oligomer having an acid anhydride at its terminal, which has a fluorene imine unit of the following formula [I], and wherein the composition ratio (A / B) of the A component and the B component is Within 1.2-5. [Formula I] ------ 5- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 574262

[Wherein A is an asymmetric aromatic tetracarboxylic dianhydride residue or an alicyclic tetracarboxylic acid dihepatic residue, and B is a diamine polysiloxane residue. ] & In addition, in the present invention, the ammonium oligomer having an acid anhydride at the end can be used as an asymmetric aromatic tetracarboxylic dianhydride residue or an alicyclic tetracarboxylic dianhydride (component A) first. Chemical agent, especially a primary alcohol having a carbon number of 4 or less, half-esterified it, and then adding diamine polysiloxane (component B) to the obtained reaction solution, so that the composition ratio (A / B) of each component becomes丨. Within the range of 2-5, finally, it is dehydrated by a single-point reaction at a temperature of less than 250 ° C above, and then made under the condition of substantially no solvent residue. Next, the present invention relates to a curable resin composition, including a fluorene-based oligomer having an acid anhydride residue at the terminal as described above, and an epoxy resin. As for "semi-acetic acid" in this specification, it refers to making tetracarboxylic acid dianhydride into a dibasic acid diester. · The present invention describes in detail the asymmetric aromatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride used to form the A component in the fluorene imine oligomer of the present invention, which can be 2, 3, 3 ', 4'-Asymmetric aromatic tetracarboxylic dianhydride such as biphenyltetracarboxylic dianhydride: or hydrogen reduction product of symmetric aromatic tetracarboxylic dianhydride, such as dicyclohexyl-6 This paper is applicable to China Standard (CNS) A4 specification (210X 297 mm) 574262 A7 B7 V. Description of the invention (4) JJ, 4,4, -tetratetracarboxylic acid dihepatitis [End of 3,3 ', 4,4'-biphenyl Tetramethyl acid is obtained through a process of hydrogen reduction-pressure heating hydrolysis-anhydrous], or an alicyclic tetracarboxylic dianhydride shown by the following [Formula II]: [Formula II]

The diamine-based polysiloxane used to form the B component in the fluorene imine oligomer of the present invention may be a diamine-based polysiloxane represented by the following [Formula III] and the like: [Formula III] H2N .R- [Si (R1) (R2) -0-] n-Si (R3) (R4) .R-NH2 (where R is a table represented by a methylene or phenylene group having 2 to 6 carbon atoms The divalent hydrocarbon group constituted; Ri, R2, r3 and r4 are lower alkyl groups or phenyl groups having a carbon number of 1-5; η is an integer of 3-60.) Specific examples of the aforementioned diaminopolysiloxane compounds, Including α, ω_bis (2_aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-amine Phenyl) polydimethylsiloxane, α, ω • bis (4-amino-3 -tolyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenyl Cornerstone oxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane, etc. In the present invention, as long as the effect of the invention is not impaired, one part of the aforementioned monoamine polyoxygen fired may be replaced with another type of diamine.

The ammonium oligomers of the present invention have acid fiber residues at the ends, and the A ΐ paper size is suitable @@ 家家 标 (CNS) A4 specifications (21G X 297 public directors) ---- 574262 A7 B7 5 2. Description of the composition ratio between the component (the aforementioned asymmetric aromatic tetracarboxylic dianhydride or alicyclic tetracarboxylic acid diresidue) and the β component (the aforementioned diaminopolysiloxane residue) (Mole The ratio) is within the range of A / B = 1.2-5. The lower limit of the aforementioned composition ratio (A / B) is preferably 1.5, the upper limit is preferably 3, and even more preferably 2. In addition, the amidine series of the present invention For oligomers, the number-average molecular weight (in terms of polystyrene) obtained through Gpc is below 10,000, preferably below 6,000. The subunit having an acid fiber residue at the end of the present invention The amine oligomer is preferably an asymmetric aromatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride (component A), first with an esterifying agent, especially a primary alcohol having a carbon number of 4 or less, After performing reflux for preferably about 0.5-24 hours, the reaction mixture is cooled to half-esterify. Then, a diamine polysiloxane ( B component), so that the composition ratio (A / B) of the two components falls within the range of i.2_5 (the lower limit is preferably 15, the upper limit is preferably 3, and the best is 2). Then under the flow of inert gas 'Remaining for the first alcohol used for hemi-acetation, and finally by a single point reaction, it is 13 (TC above 250). (: Temperature, preferably pulse 20.1%, and stir Heating for 0.5-24 hours, dehydrating, and then cooling the reaction mixture can obtain a reactant that is substantially free of solvent residues. The aforementioned acetating agent which can undergo semi-acetating reaction can have f alcoholicity OH-based compounds, such as methanol, ethanol, isopropanol, butanol, ethylene glycol ethylene acetate, propylene glycol ethyl, ethyl carbitol, etc., special carbon ... to the fatty alcohols of rhenium. Among them is the primary alcohol The best is the above-mentioned fatty alcohols with a carbon number of 4 or less. The amount of gelatin is less than the amount used for the formation of the A component relative to the mother's 100 wounds. Standard (cns) iron 297 jing ^ ------ 574262

Weight is better. The curable resin composition of the present invention can be obtained by mixing an imine-based oligomer having an acid anhydride group at the terminal as a curing agent and mixing it with an epoxy resin. Lishu epoxy resin includes all having two or more epoxy groups in the molecule. Specifically, a liquid epoxy resin having an epoxy equivalent of about 10 (M000 and a molecular weight of about 3,000 to 5000 is preferred. For example, a bisphenol a-type or bisphenol F-type epoxy resin Resin (Api-to-covering agent 806 manufactured by Japan Epoxy Resin Co., Ltd. (worker (£ j-bu 8106), Api-coating agent milk, Api-coating d 828, etc.), novolac type ring Novolac resins such as oxygen resins, cresol novolac epoxy resins; triphenol methane epoxy resins, triphenol propane cyclic emulsion resins, and other novolac epoxy resins; biphenyl epoxy resins; no bibens Structure "Varane type epoxy resin; heterocyclic type epoxy resin; epoxy resin containing naphthalene ring; stilbene type epoxy resin, etc. One or more of these materials can be used. In addition, Among the foregoing, a bisphenol eight-type epoxy resin, a bisphenol F-type epoxy resin, a biphenyl type epoxy resin, a diphenyl ethylenic epoxy resin, etc. are preferred. The hardening resin of the present invention, composition +, except The epoxy resin and the aforementioned terminal have a bismuth anhydride group (in addition to the Si imine-based oligomer, other hardeners and hardening-promoting contacts may be included). The so-called other hardeners can be alicyclic acids, varnishes, varnishes, and the like. The hardening accelerators can be stilbene, imidazole, etc. In addition, in the present invention, the solvent-free type The curable resin composition should preferably contain an alicyclic acid hydrazone-type hardener (Epi-curing agent YH306 (worker (£ 丰 a 7 YH3%)) made by Japan Epoxy Resin Co., Ltd.

Binding

-9-574262 A7 B7

The proportion of each component in the hardened resin composition of the present invention is determined based on the ratio of maintaining the composition in a liquid state at a relatively low temperature without using a solvent, and determines the amount of each component. The preferred amount is about 100-90 parts by weight based on the weight of the stone imide oligomer having an acid fiber group at the end of the epoxy resin per eight weights of epoxy resin. Secondly, when the former is contained (other hardeners (such as alicyclic acid anhydride-type hardeners), the total functional groups of the hardener are relative to the total epoxy groups per epoxy resin. It is preferably between 0.9 and L0 equivalents. Furthermore, when the aforementioned hardening accelerating catalyst is contained, the preferred content ratio is 0.1 to 10 parts by weight per 100 parts by weight of the epoxy resin. When the viscosity of the curable resin composition at 25 is within the range of 1 600 poise, it should be appropriate from the viewpoint of its operability, solution physical properties, and sealing material characteristics. The curable resin composition of the present invention Because it has the aforementioned composition and the aforementioned viscosity, if it is coated by, for example, spin coating, mask printing, dipping method, spray coating, and the like on semiconductor elements, insulating films, and conductors formed thereon, On the graphic electronic parts, after drying the film < thickness of 10-500 microns, heat it at a temperature of about 6 5-120 ° c for 30-120 minutes, and then 120_200t: heat it at a temperature of about 2_8 hours for two After the stage of heat hardening, namely It can form a sealing material with a flexural elastic modulus of 50-29 kg / cm2. Here are some examples of syntheses of the fluorene imide oligomers having acid anhydrides at the ends of the present invention, and the curable resin composition of the present invention. The examples illustrate the present invention in detail. However, the scope of the present invention is not based on such synthetic examples and actual paper sizes. The Chinese National Standard (CNS) A4 specification (210 X 297 public love) 574262 A7 B7 is used. 5. Description of the invention (

The embodiment is subject to any restrictions. In addition, the viscosity of the fluorene imide oligomer in the synthesis example was 60 with an E-type viscometer. (: Measured below. As for the viscosity measurement of the epoxy resin composition in the examples, and the bending test (measurement of flexural modulus of elasticity, breaking stress, and breaking strain) of the hardened material, it was performed as follows: [Epoxy resin combination Viscosity of material] Measured at 25 ° C using an E-type viscometer. [Bend test of hardened material] Using TENSILON UTM5T manufactured by TO YO BOLD WIN, with a range of 50 mm and a right-angle head speed of The measurement was performed under the condition of 2 mm / minute. Synthesis Example 1 A four-necked flask substituted with nitrogen was equipped with a stirrer, a nitrogen introduction tube, a reflux cooler, and a frosted glass stopper, and 37.90 g (143.4 mmol) of Great Japan was charged.彳 > Engineering made by Toyo Chemical Industry Co., Ltd. £ 口 > B4400 was used as alicyclic tetrakisine acid and 50 g of methanol and refluxed. After 3 hours, cool to room temperature and cool to reflux The device was replaced with a reflux cooler with a water separator, and an antifoaming agent [FS antifoaming agent d B -100 manufactured by Dow Corning Asia Co., Ltd.] was added. 0 · 10 g and diamine polysiloxane [East K • Made by Dow Corning Polysiloxane Amine-modified polysiloxane oil BY16-853U, that is, the compound of R = C3H6 and RrR4 = CH3 in the aforementioned formula II, the amine equivalent is 451] 64.68 g (71.71 mmol), and the methanol is distilled off in 1 hour. Then, the temperature was raised to 190 ° C, and water was allowed to react for one hour while distilling off water, to obtain 97.89 g (yield 97.90%) of a brown tea-like viscous substance (an imine oligomer of the present invention). This product (SiB) has a viscosity of 311 poise at 60 ° C. This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 574262 A7 B7 V. Description of the invention (9 Synthesis Example 2 The mouth flask was equipped with a stirrer, a nitrogen introduction tube, a reflux cooler and a ground glass stopper, and charged with 20.23 g (68.76 mmol) of 2,3,3 ', 4, biphenyltetracarboxylic dianhydride (a_BpDA), 30 grams of methanol and methanol, and refluxed. After 3 hours, cool to room temperature, replace the reflux cooler with a reflux cooler with a water separator, and add a defoamer [FS anti-foam made by Dow Corning Asia Co., Ltd. Agent DB-100] 0.07 g and diamine polysiloxane [East μ. Domineering Polyamine Modified polysiloxane oil βυ16_ 853U] 31.01 g (34_38 millimolar), methanol was distilled off in 1 hour. Then the temperature was raised to 190 C, while water was left while reacting for $ hours, ⑽πg ( (Yield 97.50%) of a tea brown viscous substance (the oligo-imide oligomer of the present invention). The viscosity of the product (SiA) at 80 ° C was 392 poise. Example 1 100 g of Japan Epoxy Resin Co., Ltd. Synthetic example of 828 and 24 grams of wormwood coating agent prepared! The obtained SiB, 116 g of the alicyclic acid anhydride type hardening part J, that is, the opiate curing agent Ni 3⑽ manufactured by Japan 3A Oxygen Resin Co., Ltd., and 1 g of hardening promotion catalyst (the maturation made by Shikoku Chemical Industry Co., Ltd. After the sol (Fujiji / Small) 2E4MZ) was mixed uniformly, it was filtered through a filter paper 408 (pore size 5 micrometers) made by ADVANTEC TOYO Co., Ltd. and subjected to a vacuum desorption method to obtain an epoxy resin composition (the hardened resin of the present invention). combination). This epoxy resin composition (viscosity: · 100 poise at 25t) was poured into a metal mold, and was cured at 100 ° C for 1 hour and 180 ° C for 5 hours to obtain a thickness of 3 mm. Thing. The bending stress of this hardened material after bending test was 3 kg / mm², the strain at break was 7.2%, and the bending elasticity was lake kg / square.

574262 A7 B7 5. Description of the invention (10) mm. Example 2 and Comparative Example Each of the epoxy resin compositions was obtained in the same manner as described in Example 1 except that the composition was as shown in [Table 1] below. Using the obtained epoxy resin composition, the cured product was evaluated in the same manner as in Example 1. The results are shown in [Table 1] below. As for the viscosity of the epoxy resin composition of Example 2, it was about 120 poise at 25 ° C. [Table 1] Example 1 Example 2 Comparative Example Epiphany Coating Agent 828 (g) 100 100 100 SiB (g) 24--SiA (g)-24-Epipurizer YH306 (g) 116 116 124 Cured Sol 2E4MZ (G) 1 1 1 Breaking stress (kg / mm²) 13 11 16 Breaking strain (%) 7.2 7.4 7.9 Flexural modulus (kg / mm²) 268 239 301 The imine oligomer of the present invention has The fluidity and the mutual solubility, if used as a hardener, can obtain a hardenable resin composition which belongs to a solvent-free type and whose hardened material exhibits low stress. ___- n This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

574262 mouth (jmm patent application μ in the patent application requested to replace the version (August 1992) c8 D8 A8 B8 «2 · 8 · 27 amended on the 27th of the date of the application for a patent scope An amine oligomer having a fluorene imine unit represented by the following [Formula 1], wherein the composition ratio (A / B) of the A component and the B component is within a range of 1.2 to 5: 〇〇— ( -ΑΑ— ν YY) 〇〇 [wherein A is an asymmetric aromatic tetracarboxylic dianhydride residue or an alicyclic tetraacid dianhydride residue, and B is a diamine polysiloxane residue. ] 2 · —An imine-based oligomer having an acid group at the end, which is prepared by the following method: an asymmetric aromatic tetracarboxylic dianhydride residue or an alicyclic tetralepic acid-Sf ( (A component) firstly esterify it with an esterifying agent, and then add diamine polysiloxane (B component) to the obtained reaction solution, so that the composition ratio (A / B) of each component is in the range of 1.2-5 In the end, at a temperature of i30 ° C or higher and less than 250 C, it is dehydrated by a single-point reaction, and then manufactured under conditions where there is virtually no solvent residue. 3. According to the second item of the scope of patent application A pyrimide-based oligomer having an acid anhydride group at the terminal, wherein the esterifying agent is a primary alcohol having a carbon number of 4 or less. 4. A curable resin composition comprising an acid anhydride group at the terminal according to item i of the scope of patent application. The imine-based oligomer and epoxy resin. 5. The hardenable resin composition according to item 4 of the scope of patent application, which further includes a hardening accelerator. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 male cage) 574262 A8 B8 C8 D8 6. Application for patent scope 6. — A hardening resin composition containing a sulfonium imide oligomer and ring with an acid anhydride group at the end according to item 2 of the patent application scope Oxygen resin. 7. The hardenable resin composition according to item 6 of the scope of patent application, which further includes a hardening accelerator. -2- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)