TW552280B - Curing agent used for epoxy resin - Google Patents

Abstract

The present invention provides a novel maleimide copolymer which is obtained from copo1ymerizing a maleimide derivative, styrene, and a maleic anhydride derivative. The maleimide copolymer can be used as the curing agent for an epoxy resin, and the cured product has a glass transition temperature higher than 150 DEG C. In addition, the curing agent also has the accelerator effect; therefore, an epoxy resin can be cured by using the curing agent alone without any additional accelerator.

Description

552280 --18811_ κYear, Month, and Day 5. Explanation of the invention (1) Description of the invention: The present invention relates to a novel maleimide copolymer, especially to an oligomerization which can be used as a hardener for% oxygen resin. The physical type maleimide imine copolymer has a hardening accelerator effect. Oxygen resin has excellent solvent resistance, mechanical strength, electrical insulation properties, good dimensional stability, and easy processing. It has been widely used in coatings, electrical insulation materials, printed circuit laminates, electronic packaging materials, civil engineering and construction. Materials, adhesives and aerospace industries. In the application of printed circuit board substrates, the resins currently used are mainly epoxy resins and acid resins. Pandemic resin is mainly used for single panel, used in consumer electronics, epoxy resin is used in multilayer boards, used in computers, instruments, etc. = grade electronic products. In response to the trend of thin and short electronic systems, high functionality, interrogation, reliability, and low cost, the development of printed circuit boards towards multilayer boards is an inevitable trend. Therefore, the amount of substrate resin currently consists of epoxy Things first. No matter in terms of quantity or technology, printed circuit board substrates are standard FR4 substrates. The traditional standard fr-4 board is an epoxy resin system. It is mainly based on Bisphenol A epoxy resin, and it is added with Diglycidyl ether of tetrabromobisphenol A (DGETBA). As the flame retardant, dicyy and i amide (DICY) was used as a hardening agent, and 2-Methylimidazole (2-MI) was used as a hardening accelerator. fr — epoxy resin system for 4 plates, the glass transition temperature (T g) of the resin after hardening is not high and uneven

552280 Amendment ^ __ Case No. 88111076_ Year ^ V. Description of Invention (2) Approximately 1 3 0. C around. However, with the rapid development of the electronics industry, various properties of substrates have become more demanding, especially in terms of high glass transition temperature, low dielectric constant, and other aspects, which have been the focus of substrate technology development in recent years. The glass transition temperature of the oxygen resin system is obviously not enough. \ In addition, considering the cost factor and the convenience of the operation, the hardening promotes the sword ϋ °, 4 <Addition is also mentioned in Japanese Patent Publication No. 1-3 0 4 1 1 2 Poly (styrene-malay) is used to react with (CH3) 2N (CH2) 3NH2 tertiary amine compound to prepare a polymerizing agent to harden epoxy resin. However, from a structural point of view, there is still a disadvantage that the Tg is not high enough. In Japanese Patent Application Laid-Open No. Sho 6 3- 0 1 7 9 5 4, poly [p-propenephenylmaleimide-styrene-maleic anhydride] is used to react with a high-molecular-weight epoxy resin to obtain heat and impact resistant Thermoplastic resin composition.

Liang et al. Used Polym. Compos · (199 9), 18 (2), 2 3 7_241 to react p-carboxylic acid (ester) phenylmaleimide with epoxy resin to prepare epoxy resin. The main bond is maleimide. This maleimide has a lower softening point and hardening temperature, and the hardened composite has higher toughness and thermal stability.

PlUpenk〇 et al. In Chem · Abs · 109: 6 3 2 060, using maleimide imine to modify the ED-20 epoxy resin can shorten the gel time of the epoxy resin. The object of the present invention is to provide a novel maleimide copolymer of maleic acid. Another object of the present invention is to solve the aforementioned epoxy resin. The disadvantage is not high enough, and a hardener for epoxy resin is provided. This hardener also has A I ′ which promotes hardening. Without the addition of a hardening accelerator, that is, {the epoxy resin undergoes a hardening reaction, and the glass of the epoxy resin after hardening

552280

The transfer temperature can be increased to 150. C or more. Another object of the present invention is to provide a thermosetting epoxy resin composition which is hardened and has a rupture of above. The composition, this high 150 ° type epoxy resin transfer temperature can be improved. In order to achieve the purpose of the present invention, the novel product of the present invention is represented by chemical formula (I) or (丨 丨), ..., "acid imine copolymerization ( maleimide derivative), styrene, and maleic anhydride derivatives obtained by copolymerization, obtained by the formula (1 1 1)

OH

Wherein R1 and R2 may be the same or different, and R3 * R4 may be the same or different;

R1, R2, R3, and R4 may be hydrogen, C1-8 alkyl, C2-8 alkeny1, C6-10 aryl, C7-15 alkylaryl, C7-15 arylalkyl, or C 3- 8 cycloalkyl; R 5 may be C1-5 alkylene, C1-8 cycloalkylene, or phenylene; and R 6 may be hydrogen or c 1-8 alkyl. The novel maleimide imine copolymer of the present invention is obtained by copolymerizing a maleimide imine derivative, styrene, and a maleic anhydride derivative. This new Malay St imine copolymer can be used as a hardener for epoxy resins. The maleimidine imine derivative used in the present invention has the formula (I) or (I I)

552280 __Case No. 88111076_ 年月 日 __ V. The structure shown in the description of the invention (4). The maleic anhydride derivative used in the present invention has a structure represented by the chemical formula (I I I).

Wherein R1 and R2 may be the same or different, and R3 and R4 may be the same or different;

R1, R2, R3, R4 may be hydrogen, C1-8 alkyl, C2-8 alkenyl, C6-10 aryl, C7-15 alkylaryl, C7-15 arylalkyl, or C 3-8 cycloalkyl; R5 may be C1-5 alkylene, C1-8 cycloalkylene, or phenylene; and R6 may be hydrogen or C1-8 alkyl. For the formula (I), when R1 and R2 are both hydrogen and R5 is a phenylene group, the formula (I) is

Preferred R 6 may be hydrogen, methyl, or ethyl. Therefore, the maleimide derivative represented by the chemical formula (I) may be phenylmaleimide carboxylate, methyl phenylmaleimide carboxylate, ethyl phenylmaleimide carboxylate, or Its mixture. According to the present invention, in order to synthesize the maleimidine imine copolymer of the present invention, a male donkey imine derivative represented by the chemical formula (I) or (I I), phenethylhydrazone, and a chemical

Page 10 King No. 881 Revision V. Description of the invention (5) ____ Restriction on maleic anhydride-derived hydrazone represented by formula (I I I). The preferred dosage is not from 1 to 30 mole percent. The amount of benzene to make imine derivatives is i, t is 0 to 6 / 布, and the derivative is 20 to 6. 〇 Molar percentage into heteroauric percentage, the maleic anhydride oxy resin hardener, the number S ° synthesized polymer can be used as a ring due to the synthesis of the horse 10_ &quot; 〇_. Therefore, the bamboo shoots can be used as the epoxy resin, which includes-epoxy; = solid epoxy resin composition

.1 π. 4, sl, ^ V The maleic anhydride derivative of the formula (II I) is co-preprepared as a hardener. The use of this hardening agent σ in the target field is 0.5 to more than the epoxy group equivalent of the oxygen resin. The functional group equivalent of the so-called hardener is the sum of the equivalent of carboxyl group (carboxyl 6) or hydroxyl group. 5 (0 Η) and anhydride group. The epoxy resin suitable for use in the present invention is not particularly limited, as long as the epoxy resin can be subjected to a hardening reaction using the hardener of the present invention. For example, moxibustion such as an epoxy tree can be a variety of epoxy resins, a double S-type A (bisphen〇i epoxy resin, or a varolak) epoxy resin, etc. Using the hardener of the present invention (that is, Maleimide imine copolymer), can harden the epoxy resin composition without adding any hardening accelerator. However, in order to make the hardening reaction faster, it can also be used in epoxy resin. An additional hardening accelerator is added to the composition, and the amount can be from 0. 0 1 to 3 weight percent for the epoxy resin. Examples of the hardening accelerator include imidazole compounds, three-grade Yuean dagger Compounds, phosphine compounds, cycloamidine 552280 (Case No. 88111076, fifth, description of the invention (6) compounds), etc. The hardener provided by the present invention can be obtained from other sources. μ J has been used alone or blended earlier. Therefore, the hardening agent provided by the epoxy tree of the present invention is different from the hardening agent of the modified fat composition, which makes the functional group of the hardening agent as the $ &gt; &amp; 田 ϊ 0 · 5 to 1 · 5 times the epoxy tree. This second hard &gt; [Bu Ru l 10 Sergeant, the culture agent may be an amine hardener, or a self-clearing varnish hardener, etc. The scope of the present invention also includes the product consisting of the above-mentioned alternatives and the lice resin. With the special &lt; hardener of the present invention, the hard glass transition temperature can be as high as 50 ° C. or higher. This grease can be applied to electronic component packaging materials and laminated sheets. The following examples are given to illustrate the present invention in more detail. The point 'is not intended to limit the present invention, and the scope of patent application of the present invention shall prevail. It is manufactured by Chun Artificial Resin Company added in the following examples, and its trade name is BeB- [brominated diglycidyl ether of 2, hydroxyphenyl) propane], Epoxy equivalent and other hardening include epoxy resin with fat of the second hardener, epoxy hardening obtained by hardening and inversion of epoxy anhydride, and various coating methods, and the characteristic range should be based on the epoxy resin. 530-A-80 2 '-bis (4- is 410-460c agent to make the amount of equivalent hardening of the invention should be equivalent to the epoxy resin epoxy resin packaging materials and excellent applications are long [Example 1] Take 20.8g of styrene (0.2mole), maleic anhydride 9.8g (〇mole), p-carboxylic acid benzene maleimide imide 21.7g (Ojmole), dissolved in i20ma ethyl ethyl group and dimethylacetamidine The amine mixed solvent (volume ratio 5 / 丨) was placed in a 500mira port reactor equipped with a mechanical stirring tube, a condensing tube, a nitrogen gas tube, and a feeding port. The temperature was raised to 75 ° C, and then 552280 case number 88111 dissolved in an appropriate amount of methyl ethyl ketone f) 7fi V. Description of the invention (7) 3.2 g azobisisobutyl (AIM; az〇blSls〇butyr〇nitrlle) was added

In the DSC reaction, the temperature was maintained at 70 to 80 ° C, and the reaction was performed for 5 hours. After the reaction and the end, it was precipitated with a large amount of water, washed, and placed in a 60 ℃: drying in a vacuum oven to obtain the product, and the number average molecular weight was measured by GPC to be 6,000 g / mole. / min) Glass transition temperature Tg = 2 2 5Ό [Example 2] The procedure is the same as in Example 丨, but 0.4 § dodecyl mercaptan was added to the methyl ethyl ketone solution of azobisisobutyl. The number unevenness of the product was measured by GPC, and the molecular weight was 300 g / mole. The glass transition temperature T g = 198 ° C was measured by DSC (temperature increase rate: 20 C / min). [Example 3] The procedure is the same as in Example 1 except that the molar ratio of stupid ethylene-maleic anhydride to carboxylic acid phenylmaleimide is changed, and the amount is 31.2 g (0.3 mole) of styrene. 1.9 g of maleic anhydride (0.2 mo 1 e) and 21.7 g (0.1 mole) of p-carboxylic acid phenylmaleimide. The number-average molecular weight of the product measured by GPC was 2750 g / mole, and the glass transition temperature Tg = 17 7 was determined by DSC (temperature rise rate 20 ° C / min). (3.

[Example 4] 3 g of epoxy resin and the poly (styrene ~ wild maleic acid-maleic acid fc imine) obtained in Example 1> cereal solution were mixed in an equivalent ratio, and mixed into a homogeneous spoon. , The solution, poured into an aluminum pan, remove the solvent in a vacuum oven of 6 (TC,-dry corpse, film. This film is placed in an oven at 50 ° C for 2 hours, and then into

552280 Case No. 88111076 A_η Revision V. Description of the invention (8) C / m i η Harden for 2 hours. The hardened material was measured by DSC (Heating rate 2 (T glass transition temperature Tg = 161 ° C. [Example 5] The procedure is the same as in Example 4, but the poly (styrene-maleic anhydride- P-carboxylic acid phenylmaleimide) as a hardener. The material after hardening is measured by DSC (temperature rise rate 20 ° C / min) and its glass transition temperature Tg = 16 50 ° C. [Example 6] The formulation is the same as the implementation Example: 3 g of epoxy resin and the poly (styrene-maleic anhydride-carboxylic acid phenylmaleimide) solution obtained in Example 1 were mixed in an equivalent ratio and stirred to form a uniform transparent solution. 0 5 g 2 At temperatures of ° C, 1 3 0 ° C, and 150 ° C, the gel time was tested and the results are shown in Table 1. [Example 7] The procedure was the same as in Example 6, except that 0.50 g 2 was added to the formula. -Methylimidazole (2_methy 1 imida ζ ο 1 e). The results of the gel time test are shown in Table 1. See [Example 8] The formula is the same as in Example 5, and 3 g of epoxy resin was obtained from Example 3. The poly (styrene-maleic anhydride and carboxylic acid phenylmaleimide) solution is mixed in an equivalent ratio and stirred to form a uniform transparent solution. The gel time was tested at 0 ° C, 130 ° C and 150 ° C. The results are shown in Table 1.

Page 552280 Correction

Case No. 881110 ^ V. Description of the invention (9) [Example 9] The procedure is the same as that in Example 8, but 0.05 g of 2-methylimidazole is added to the formula. The gel time test results are shown in Table 1. [Comparative Example 1] 3 g of epoxy resin and hardener DICY (Tokyo chemical ratio was dissolved in dimethyl ethyl amine solvent, and 0.1 lwt) bisimidazole was added, and the mixture was stirred to form a uniform transparent solution. Make this solution. Soil c, 130. c. 15 (r C) The gel time was measured. The results are shown in Table 1. In addition, the solution was poured into an aluminum pan, and the solvent was removed in a 6 ot: vacuum oven and dried to form a film. This film was placed in an oven. It was hardened for 2 hours at 15 and 2 hours at i 8 0. The hardened material was measured by DSC (temperature rise rate 20). C / mi glass transition temperature Tg = 1 3 0. (3. η ^ [Comparative implementation Example 2] 3 g of epoxy resin and hardener s MA (styrene-c 〇- ma 1 eimide

EF30 (Elf Atochem) was dissolved in a dimethylamine solvent at an equivalent ratio, and then 0.1% by weight of dimethylimidazole was added and mixed to form a uniform transparent solution. The results of the test gel time are shown below in (丨 (TC, 1 3 (rc, 1 5 (TC) are shown in Table 1. From the above results, it can be seen that the hardening agent of the present invention is used to harden the epoxy resin.) The product obtained has a higher glass transition temperature than those obtained using conventional D CY or SMA hardeners. Moreover, using the hardeners of the present invention, the gel time is different with or without the addition of a hardening accelerator. 'Not big' means that the hardener of the present invention can be used without the addition of a hardening accelerator.

Page 552 280

1. Description of the invention (10) _ 1 / Under the effective curing of epoxy resin. 4, "In the case where no hardening accelerator is added, :: day ': know hardening is long. 1 The spinning time is very much. Although the present invention has been compared with the present invention, within any familiarity range, when the attached patent application form can be made as a preferred embodiment, the above-mentioned skilled person will be disclosed. The ones defined shall prevail. ’However, it is not intended to limit the scope of the invention without departing from the spirit and scope of the invention.

Hot 13 0 ° c 15 0 ° C ^ Example 6 The polymer obtained in Example 1 is not available> i〇min2 9 5 secl35sec Example 7 The polymer obtained in Example 1 is available> 10 min28 0sec 110 seconds &gt; Example 8 does not include the polymer paid in Example 3 &gt; 10min320secl30sec The polymer obtained in Example 3 of Binsch Example 9 has &gt; IQ min260secl00sec Comparative Example 1DICY Yes &gt; 10 min &gt; 10 min350sec Example 2 SMA has> 10 min> 10 min 405 sec *: Place the sample on a hot plate at a set temperature, circle with a Teflon rod, and try drawing until the rubber wire breaks.

Page 16 552280 _Case No. 88111076_ Year Month Day _ Amendment

Page 17

Claims (1)

552 Announcement 銮 j 88111076 Amendment of the month ........., year ΕΠ 6. Scope of patent application --- --- J 1. A hardener for epoxy resin, which is represented by the chemical formula (I) or (II) The maleimide imide derivative, styrene, and the maleic anhydride derivative represented by the chemical formula (III) are copolymerized by a maleimide imine copolymer, COOR6 ί: (III) 0 &lt; &gt; = 0 〇 where R and R may be the same or different, and R and R may be the same or different; R1, R2, R3, R is R, C, -Cryl, C2-alkenyl, or C 3-cycloalkyl; R may be C 丨 -alkylene, C 丨 _cycloalkylene, or phenylene; and R is 氲 or (: 丨 _ alkyl; the maleimidine imine derivative The amount of the substance is 1 to 30 mole percent, styrene is 30 to 65 mole percent, and maleic anhydride derivative is 20 to 60 mole percent; the number average molecular weight is 100 to 0 0 0 0 0. 2. The hardener as described in item 1 of the scope of patent application, wherein both R and R are 氲. 3. The hardener as described in item 2 of the scope of patent application, wherein R 5 is sub- Phenyl 4. As the scope of patent application The hardener of item 1, wherein the malayan Page 18 552280 _ Case No. 88111076 _ Amendment _ Sixth, the scope of the patent application for the amine derivative is selected from free carboxylic acid benzomaleimide, methyl carboxylate phenylmaleimide, ethyl carboxylic acid benzene In the group consisting of maleimidine imine and mixtures thereof, the hardening agent as described in item 4 of the scope of the patent application, wherein the maleimide derivative is phenylmaleimide p-weilate. 6. The hardener according to item 1 of the scope of patent application, wherein R and R are both hydrogen. 7. A thermosetting epoxy resin composition comprising an epoxy resin and a hardener as described in item 1 of the scope of patent application, wherein the amount of the hardener is such that the functional group equivalent of the hardener is the The epoxy group has an epoxy equivalent of 0.5 to 1.5 times. 8. The epoxy resin composition as described in item 7 of the scope of patent application, wherein the epoxy resin is a selective S-class epoxy resin, a biphasic A type (bisphe η ο 1 A) bad emulsion resin 'and a varnish type (Novolak) ¾ milk group month purpose of the group 〇9. As described in the scope of the patent application for the epoxy resin composition described in item 7, which further includes a hardening accelerator, accounting for the epoxy resin amount of 0. 0 1 to 3 weight percent. 10. The epoxy resin composition according to item 9 of the scope of the patent application, wherein the hardening accelerator is selected from the group consisting of selective imidazole compounds, tertiary amine compounds, phosphine compounds, and cyclofluorene compounds. 1 1. The epoxy resin composition according to item 7 of the scope of patent application, further comprising a second hardener, which is different from the hardener described in item 1 of the scope of patent application, wherein the amount of the second hardener is Make the function of the second hardener Page 19 552280 Case No. 88111076 Said amendment ~, patent application scope The base equivalent is 0.5 to 1.5 times the epoxy equivalent of the epoxy resin. 1 2. The epoxy resin composition according to item 11 of the scope of the patent application, wherein the second hardener is selected from the group consisting of amine hardener, acid anhydride hardener, and novolac hardener. . Page 20