CN100453593C - Difficult combustible epoxy resin composition not containing halogen - Google Patents
Difficult combustible epoxy resin composition not containing halogen Download PDFInfo
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- CN100453593C CN100453593C CNB2005101175080A CN200510117508A CN100453593C CN 100453593 C CN100453593 C CN 100453593C CN B2005101175080 A CNB2005101175080 A CN B2005101175080A CN 200510117508 A CN200510117508 A CN 200510117508A CN 100453593 C CN100453593 C CN 100453593C
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Abstract
This invention relates to a halogen-free uninflammable epoxy resin composition, which comprises: epoxy resin, hardening agent, hardening accelerator, toughening agent and inorganic fillers. The halogen-free uninflammable epoxy resin composition has good heat resistance and good adhesive effect, and can be used as adhesive for soft printed circuit boards.
Description
Technical field
The relevant a kind of not halogen-containing difficult combustible epoxy resin composition of the present invention, especially relevant a kind ofly have high heat resistance, high then property and can use not halogen-containing difficult combustible epoxy resin composition as the solid of flexible circuit board.
Background technology
Along with the lightweight and the miniaturization of electronic product, in many designs, be partial to the use flexible printed wiring board, so that the degree of freedom of space configuration and electronic component installation etc. to be provided.
And flexible printed wiring board; is example with Copper Foil as substrate; generally coating one solid on a plastic film on making; Copper Foil is sticked on the plastic film; the circuit pattern that forms according to the institute desire subsequently; Copper Foil is carried out etching form required circuit, subsequently for fear of the metal wire oxidation, the mulch film that is covered is again usually protected this flexible printed wiring board.
Owing to form in this kind flexible printed wiring board process, the step that must at high temperature toast is arranged, therefore used plastic film and employed solid generally needs characteristics such as thermotolerance and dimensional stability.Wherein, generally use Kapton in the industry as plastic film.
At present institute for acquisition high heat resistance and flame retardancy, uses the halogen-containing or stibiated composition epoxy resin of halogen-containing incombustible agent in order to make the solid of flexible circuit board more.These incombustible agents or composition epoxy resin can discharge as toxic gases such as dioxins when burning, and cause problem of environmental pollution.
Along with the lifting of environmental protection consciousness, many concept developments in the exploitation of many materials towards environmental protection.For this reason, the invention is intended to provide a kind of and meet the environmental protection demand, reduce the composition epoxy resin of environmental pollution and excellent heat resistance and can be applicable to make soft and hard printed circuit board.
The inventor etc. are through broad research, test, thereby finish the present invention.
Summary of the invention
The relevant a kind of not halogen-containing difficult combustible epoxy resin composition of the present invention, especially relevant a kind ofly have high heat resistance, high then property and can use not halogen-containing difficult combustible epoxy resin composition as the solid of flexible circuit board.
The relevant a kind of not halogen-containing difficult combustible epoxy resin composition of the present invention, it comprises: (a) Resins, epoxy; (b) toughner; Reach (c) incombustible agent;
Wherein this Resins, epoxy (a) is for being selected from least a or its mixture of Resins, epoxy (a1) and Resins, epoxy (a2):
(a1) derived from the Resins, epoxy of the compound reaction gained shown in phenolic compound shown in the following formula (I) and the formula (II) with 2 epoxide functional groups:
[wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer];
[wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer];
The ratio (H1/E1) of the epoxide equivalent (E1) of the compound with 2 epoxy group(ing) shown in the Ahew (H1) of the phenolic compound shown in its Chinese style (I) and the formula (II) is in 0.6 to 1.2 scope;
(a2) derived from the Resins, epoxy of the compound reaction gained shown in compound shown in the phenolic compound shown in the following formula (I), the formula (II) and the formula (III) with 4 or 4 above epoxide functional groups with 2 epoxy group(ing):
[wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer];
[wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer];
[wherein A represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
3For identical or different and represent C
1-6Alkyl or hydroxyl; C represents 0 to 2 integer; N is the integer of 0-20];
The Ahew (H1) of the phenolic compound of its Chinese style (I) and the epoxide equivalent (E1) of the compound with 2 epoxy group(ing) of formula (II) and the scope of ratio [H1/ (E1+E2)] 0.4 to 2.0 of epoxy equivalent (weight) (E2) sum total of the compound shown in the formula (III), 0.6 to 1.2 scope more fortunately with 4 or 4 above epoxide functional groups;
Wherein in (a) and (b) and (c) gross weight be 100 weight %, (a) composition accounts for 35～60 weight %, (b) composition accounts for 25～40 weight %, and (c) composition accounts for 15～25 weight %.
Not halogen-containing difficult combustible epoxy resin composition of the present invention comprises (d) stiffening agent, (e) hardening accelerator and (f) inorganic filler again, the amount of (d) stiffening agent wherein, in Ahew, be 0.2～5 part of the epoxy equivalent (weight) of relative Resins, epoxy (a), (e) amount of hardening accelerator, be 0.1～1 weight % with respect to Resins, epoxy (a) weight, (f) amount of inorganic filler then reaches (c) 2～10 weight % of gross weight for accounting for (a) and (b).
Embodiment
Measure the weight average molecular weight (Mw) that is scaled polystyrene as Resins, epoxy used among the present invention (a1) in GPC (gel permeation chromatography) and be about 700 to 20000 scope, more preferably 1000 to 15000 scope.The epoxy equivalent (weight) (EEW) that Resins, epoxy (a1) is measured according to the standard of ASTM D1652 is in 700 to 1500g/eq scope, better in 900 to 1200g/eq scope.
Measure the weight average molecular weight (Mw) that is scaled polystyrene as Resins, epoxy used among the present invention (a2) in GPC (gel permeation chromatography) and be about 3000 to 28000 scope, more preferably 5000 to 22000 scope.The epoxy equivalent (weight) (EEW) that Resins, epoxy (a2) is measured according to the standard of ASTM D1652 is in 700 to 1500g/eq scope, better in 900 to 1200g/eq scope.
C shown in the A of the Y of the Z of the formula (I) of definition Resins, epoxy, formula (II) and formula (III) among the present invention
1-6Stretch the alkyl of stretching that alkyl can be straight chain or branched chain, for example methylene radical, stretch ethyl, stretch propyl group, stretch butyl, stretch amyl group, stretch hexyl, dimethylated methylene base, methyl methylene radical and isomery base thereof etc.
In the Resins, epoxy of the present invention, phenolic compound shown in the formula (I) can be given an example as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4,4 '-xenol, 3,3 '-dimethyl-4,4 '-xenol, and 3,3 ', 5,5 '-tetramethyl--4,4 '-xenol.
In the Resins, epoxy of the present invention, the Resins, epoxy example shown in the formula (II) comprises for example phenolic aldehyde polyglycidyl ether, cresols phenolic aldehyde polyglycidyl ether, bisphenol-A phenolic polyglycidyl ether, or its mixture.
In the Resins, epoxy of the present invention, the Resins, epoxy shown in the formula (III) is to be derived and get through condensation polymerization by formula (I) compound.
Toughner example as (b) composition used among the present invention, can give an example as (but being not limited to) acrylic-nitrile rubber, divinyl rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, have carboxyl end groups rubber, have amine-terminated rubber, have the rubber, silicone rubber, polyacrylic rubber of terminal epoxy groups etc., it can be used alone or with two or more and use.
Incombustible agent example as (c) composition used among the present invention; can give an example as (but being not limited to) OP-930, OP935 (trade(brand)name; available from Clariant limited-liability company), MPP (trade(brand)name; see glad Industry Co.,Ltd available from Taiwan), SPE-100, SPB-100 (trade(brand)name is available from Japan big tomb chemistry limited-liability company).
As the stiffening agent example of (d) composition used among the present invention, can give an example as (but being not limited to) Dyhard RU 100 (DICY), bisphenol resin, polyhydroxy phenol resin, phenolic and acid anhydrides etc.The example of bisphenol resin for example comprise compound shown in the formula HO-Ph-X-Ph-OH (wherein phenyl is stretched in the Ph representative, the X=chemical bond ,-CH
2-C (CH
3)
2-, O, S ,-CO-or-SO
2-), specific examples is for example tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4 ', 4 '-Lian phenol, 3,3 '-dimethyl-4,4 '-Lian phenol or 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian phenol etc.Polyhydroxy phenol resin specific examples comprises for example ginseng (4-hydroxy phenyl) methane, ginseng (4-hydroxy phenyl) ethane, ginseng (4-hydroxy phenyl) propane, ginseng (4-hydroxy phenyl) butane, ginseng (3-methyl-4-hydroxy phenyl) methane, ginseng (3,5-methyl-4-hydroxy phenyl) methane, four (4-hydroxy phenyl) methane or four (3,5-dimethyl-4-hydroxy phenyl) methane etc.The specific examples of phenolic comprises for example phenol formaldehyde condensate, cresols phenolic condensation compound, bisphenol-A phenolic condenses or dicyclo amylene-phenolic condensation compound etc.The specific examples of anhydrides for example comprises 3,3 ', 4,4 '-benzophenone tetracarboxylic acid anhydride (3,3 ', 4,4 '-benzophenone-tetracarboxylic dihydride) (BTDA), trimellitic acid 1,2-anhydride (trimellitic acid anhydride) (BTDA) and Pyromellitic Acid dicarboxylic anhydride (pyromellitic aciddihydride) etc.
As the hardening accelerator example of (e) composition used among the present invention, can give an example as (but being not limited to) tertiary amine, three grades of phosphines, quarternary ammonium salt, microcosmic salt salt, boron trifluoride misfit thing, lithium compound or imidazolium compounds or its mixtures.The tertiary amine specific examples comprises for example Trimethylamine 99, triethylamine, diisopropylethylamine, dimethylethanolamine, xylidine, ginseng (N, N-dimethyl amine ylmethyl) phenol or N, N-dimethyl amido methylphenol etc.Three grades of phosphine specific exampless comprise triphenyl phosphine etc.The quarternary ammonium salt specific examples comprises for example Tetramethylammonium chloride, tetramethylammonium bromide, chlorination triethylbenzene ammonium methyl, bromination triethylbenzene ammonium methyl or iodate triethylbenzene ammonium methyl etc.The microcosmic salt specific examples comprises chlorination tetrabutyl microcosmic salt, bromination tetrabutyl microcosmic salt, iodate tetrabutyl microcosmic salt, tetrabutyl phosphoric acid salt acetate misfit thing, tetraphenylphosphonium chloride salt, the tetraphenylphosphonibromide bromide microcosmic salt, iodate tetraphenyl microcosmic salt, tonsilon triphenyl microcosmic salt, bromination ethyl triphenyl microcosmic salt, iodate ethyl triphenyl microcosmic salt, ethyl triphenyl phosphoric acid salt acetate misfit thing, ethyl triphenyl phosphoric acid salt phosphoric acid salt misfit thing, chlorination propyl group triphenyl microcosmic salt, bromination propyl group triphenyl microcosmic salt, iodate propyl group triphenyl microcosmic salt, chlorinated butyl triphenyl microcosmic salt, bromination butyl triphenyl microcosmic salt or iodate butyl triphenyl microcosmic salt etc.The imidazolium compounds specific examples comprises for example glyoxal ethyline (2-MI), 2-phenylimidazole or 2-ethyl-4-methylimidazole (2E4MI) etc.These hardening accelerators can multiple alone or in combination use.
Inorganic filler example as (f) composition used among the present invention, can give an example as (but being not limited to) crystalline silica, fused silica, aluminium hydroxide, magnesium hydroxide, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, aluminum oxide, magnesium oxide, weisspiessglanz, zinc oxide, titanium oxide, talcum, diatomite, clay, mica, trimeric cyanamide pyrophosphate, trimeric cyanamide poly phosphate, MPP (trade(brand)name, see glad Industry Co.,Ltd available from Taiwan) and OP-930, OP935 (trade(brand)name is available from Clariant limited-liability company) etc.
The present invention will further be illustrated with the following example.These embodiment are only in order to explanation the present invention, and not in order to limit the scope of the invention.
In the following example, relevant to follow the test method of strength trial, heat-resisting scolding tin test, flexure test and flame retardancy test by the Copper Foil of the flexible printed wiring board that halogen-containing composition epoxy resin obtained of the present invention not as follows:
1. Copper Foil is followed strength trial
Enforcement of regulations according to IPC TM-6502.4.9.At first flexible circuit board is cut into 2 centimeters * 15 centimeters sample, get two samples, every is sticked two on anti-etching adhesive tape, again through etching, with washing, oven dry, fit with impregnation film (prepreg) again, at last to peel off the test machine test, strippable value is Copper Foil and follows intensity, represents with kgf/cm.
2. heat-resisting scolding tin test
Enforcement of regulations according to IPC-TM-6502.4.13.At first flexible circuit board is cut into the sample of 3 inch * 7 inch, get two samples, coat soldering flux at copper face, toasted 1 hour down at 135 ℃ then, at last 288 ℃ tin stove test and measure to observing that the polyimide face bubbles or time during demixing phenomenon, the measured time is in second.
3. flexility test
Enforcement of regulations according to IPC-TM-6502.6.18.At first the copper-clad surface with single sided board presses dried etchant resist, then puts egative film, behind overexposure, development, etching, stripping, tests with pendulum folding trier, and the gained flexility is represented with the bending number of times when rupturing in hundred folding trier.
4. flame retardancy test
The flame retardancy test is the V-0 specification according to UL 94 (Underwriters Laboratory Subject 94), implements testing vertical flammability.Particularly, prepare 5 test films, so that the mode of test film approximate vertical, point is fought and was kept for 10 seconds below test film.Then lighted a fire again for 10 seconds at once if flame disappears, withdraw flame subsequently.After the first time and refire time end, arranged if finish in 10 seconds that all flame is arranged the time of flame sustained combustion, it is qualified then to judge; And refire time have flame time length and non-flaming combustion time length total if 30 seconds with interior then be judged to be qualified; And the time that flame is arranged of 5 test films be aggregated in 50 seconds with interior then judge qualified.
Preparation example 1
The preparation of Resins, epoxy (a1):
Dihydroxyphenyl propane 88.4 gram and bisphenol A diglycidyl ether 200.0 are restrained in the 1 liter of 5 neck glass reaction bottle internal heating that is equipped with heating mantles, temperature regulator, electric blender and stirring rod, nitrogen inlet, electroheat pair, water cooled condenser and feed hopper stir, stirred 1 hour after then making temperature reach 120 ℃ until contents melting.In the gained mixture, add catalyst 10% triphenylphosphine 0.2 gram, 170 ℃ temperature heated and stirred reactions 2 hours.
Remove heating mantles and be cooled to 120 ℃, the react product Resins, epoxy that obtains is let out in the aluminium dish.After cooling is solidified, obtain Resins, epoxy of the present invention (a1) 288.6 grams of white transparent solid, in the present invention, be called BE504, measure its epoxy equivalent (weight) and be about 950-1000g/eq.
Preparation example 2
The preparation of Resins, epoxy (a2):
Make the Resins, epoxy (R wherein of dihydroxyphenyl propane 102.2 gram and structure shown in bisphenol A diglycidyl ether 200.0 grams and the above-mentioned formula (III)
3Be hydrogen and A representative-C (CH
3)
2-group, epoxy equivalent (weight) (EEW)=200) 33.6 restrains in the 1 liter of 5 neck glass reaction bottle internal heating that is equipped with heating mantles, temperature regulator, electric blender and stirring rod, nitrogen inlet, electroheat pair, water cooled condenser and feed hopper and stir, stirred 1 hour after then making temperature reach 120 ℃ until contents melting.In the gained mixture, add catalyst 10% triphenylphosphine 0.2 gram, 170 ℃ temperature heated and stirred reactions 2 hours.
Remove heating mantles and be cooled to 150 ℃, the product Resins, epoxy that is obtained is let out in the aluminium dish.After cooling is solidified, obtain white transparent solid Resins, epoxy of the present invention (a2) 352.2 grams.Be called BE1000 in the present invention, epoxy equivalent (weight) is about 1002g/eq.
Embodiment 1
In 300 milliliters beaker, at room temperature first aluminium hydroxide 3.0 grams, incombustible agent OP930 15.0 with inorganic filler restrains in methyl ethyl ketone (MEK) 200.0 grams as solvent and stirred 30 minutes, then add the prepared Resins, epoxy (BE1000 of above-mentioned preparation example in regular turn, epoxy equivalent (weight) weight (EEW) 1002 gram/equivalents) 40.0 grams and Resins, epoxy (BE 504, and epoxy equivalent (weight) weight is 950-1000 gram/equivalent) 5.0 restrain and stirred 30 minutes.Add resol PF6300 (nitrogenous resol again, make by Changchun Artificial Resin Factory Co. Ltd., nitrogen content is 16%) 15.0 grams, stirred 20 minutes, add not only toughner acrylonitrile-butadiene rubber 25.0 grams and but also stirred 30 minutes, add stiffening agent Dyhard RU 100 (Dicyandiamide, DICY) 0.8 gram and hardening accelerator glyoxal ethyline (2-MI) 0.2 gram at last, stirred 15 minutes, and obtained the composition epoxy resin that solid type part about 33% and viscosity are about 783cps.
The gained composition epoxy resin coated on the Apical Kapton (KANEKAHIGH-TECH.MATERIALS INC. manufacturing) with the line rod become 25 microns of thickness, baking is 3 minutes in 80 ℃ of baking ovens, removed solvent in 3 minutes in 140 ℃ of bakings again, after removing solvent, coated film thickness becomes 15 microns, again with JE RA 1/2OZ Copper Foil in 180 ℃ with 100kg/cm
2Hot pressing 10 minutes was put into 180 ℃ of baking oven bakings again 1 hour and in 220 ℃ of baking oven bakings post-hardening in 2 hours, was obtained flexible printed wiring board.
The flexible printed wiring board of gained carries out above-mentioned Copper Foil and follows strength trial, heat-resisting scolding tin test, flexure test and flame retardancy test, the results are shown in table 2.
Embodiment 2～7 and comparative example 1～2
Prepare the composition epoxy resin of embodiment 2～7 and comparative example 1～2 according to each composition shown in the following table 1 and ratio according to embodiment 1 resin method, and prepare flexible printed wiring board according to embodiment 1 described program.
The flexible printed wiring board of each embodiment and comparative example gained carries out above-mentioned Copper Foil and follows strength trial, heat-resisting scolding tin test, flexure test and flame retardancy test, the results are shown in table 2.
Table 1
Annotate:
1) BEP 318 makes the phosphorous epoxy resin that sells for Changchun Artificial Resin Factory Co. Ltd., and phosphorus content is 2.3-2.6%, and epoxy equivalent (weight) is 480 gram/equivalents.
2) BEP 330 makes the phosphorous epoxy resin that sells for Changchun Artificial Resin Factory Co. Ltd., and phosphorus content is 3.3%, and epoxy equivalent (weight) is 380 gram/equivalents.
3) PF-6300 is that Changchun Artificial Resin Factory Co. Ltd. makes the nitrogenous resol that sells, and nitrogen content is 16%
4) OP-930 system is available from the incombustible agent of the organophosphate of German Clariant company.
5) MPP is a melamine polyphosphate incombustible agent of seeing glad Industry Co.,Ltd available from Taiwan.
6) SPE-100 is the anti-right agent of phosphorous nitrogen available from Japan big tomb chemical industry limited-liability company.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | |
| Stripping strength (kgf/cm) | 1.78 | 1.65 | 1.34 | 1.6 | 1.43 | 1.42 | 1.53 | 1.24 | 1.03 |
| Thermotolerance (second) | 232 | 289 | 215 | 254 | 245 | 305 | 208 | 134 | 185 |
| Flexility | 28827 | 27150 | 29823 | 31845 | 33254 | 26894 | 28743 | 23425 | 21852 |
| Flame retardancy UL-94V0 | By | By | By | By | By | By | By | By | By |
By the analytical data of last table 2 gained as can be known, have than by the prepared soft and hard printed circuit board of phosphorated composition epoxy resin (comparative example 1 and 2) as the prepared flexible printed wiring board of solid according to not halogen-containing composition epoxy resin of the present invention (embodiment 1-7), better stripping strength is arranged, and thermotolerance and flexility all are better than comparative example, and flame retardancy also similarly meets the grade of the V0 of UL-94 institute standard.
According to not halogen-containing composition epoxy resin of the present invention, by containing Resins, epoxy of the present invention, can under not halogen-containing situation, reach and make required stripping strength, thermotolerance, flexility and the flame retardancy of flexible printed wiring board, and be suitable as the solid of printed circuit board (PCB).And composition epoxy resin of the present invention can fully reach environmental protection requirement because of not halogen-containing.
Claims (6)
1. not halogen-containing difficult combustible epoxy resin composition, it comprises: (a) Resins, epoxy; (b) toughner; Reach (c) incombustible agent;
Wherein this Resins, epoxy (a) is for being selected from least a or its mixture of Resins, epoxy (a1) and Resins, epoxy (a2):
(a1) derived from the Resins, epoxy of the compound reaction gained shown in phenolic compound shown in the following formula (I) and the formula (II) with 2 epoxide functional groups:
Wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer;
Wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer;
The ratio (H1/E1) of the epoxide equivalent E1 of the compound with 2 epoxy group(ing) shown in the Ahew H1 of the phenolic compound shown in its Chinese style (I) and the formula (II) is in 0.6 to 1.2 scope;
(a2) derived from the Resins, epoxy of the compound reaction gained shown in compound shown in the phenolic compound shown in the following formula (I), the formula (II) and the formula (III) with 4 or 4 above epoxide functional groups with 2 epoxy group(ing):
Wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer;
Wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer;
Wherein A represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
3For identical or different and represent C
1-6Alkyl or hydroxyl; C represents 0 to 2 integer; N is the integer of 0-20;
The scope of ratio [H1/ (E1+E2)] 0.4 to 2.0 of the epoxy equivalent (weight) E2 sum total of the compound shown in the epoxide equivalent E1 of the compound with 2 epoxy group(ing) of the Ahew H1 of the phenolic compound of its Chinese style (I) and formula (II) and the formula (III) with 4 or 4 above epoxide functional groups;
Wherein in above-mentioned (a) and (b) and (c) gross weight be 100 weight %, above-mentioned (a) composition accounts for 35～60 weight %, above-mentioned (b) composition accounts for 25～40 weight %, and above-mentioned (c) composition accounts for 1 5～25 weight %;
Wherein to measure the weight average molecular weight Mw be scaled polystyrene in gel permeation chromatography GPC be 700 to 20000 scope to this Resins, epoxy (a1), and the epoxy equivalent (weight) EEW that measures according to the standard of ASTM D1652 is in 700 to 1500g/eq scope;
Wherein to measure the weight average molecular weight Mw be scaled polystyrene in gel permeation chromatography GPC be 3000 to 28000 scope to this Resins, epoxy (a2), and the epoxy equivalent (weight) EEW that measures according to the standard of ASTM D1 652 is in 700 to 1500g/eq scope.
2. composition epoxy resin as claimed in claim 1, it comprises (d) stiffening agent, (e) hardening accelerator and (f) inorganic filler again, the amount of (d) stiffening agent wherein, in Ahew, be 0.2～5 part of the epoxy equivalent (weight) of relative Resins, epoxy, (e) amount of hardening accelerator is 0.1～1 weight % with respect to weight epoxy, and (f) amount of inorganic filler then reaches (c) 2～10 weight % of gross weight for accounting for (a) and (b).
3. Resins, epoxy is the Resins, epoxy derived from the compound reaction gained with 2 epoxide functional groups shown in phenolic compound shown in the following formula (I) and the formula (II):
Wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer;
Wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer;
The ratio (H1/E1) of the epoxide equivalent E1 of the compound with 2 epoxy group(ing) shown in the Ahew H1 of the phenolic compound shown in its Chinese style (I) and the formula (II) is in 0.6 to 1.2 scope.
4. Resins, epoxy as claimed in claim 3, it has to measure with gel permeation chromatography GPC and is scaled the weight average molecular weight Mw that polystyrene is counted 700 to 20000 scopes, and the epoxy equivalent (weight) EEW in 700 to 1500g/eq scopes that measures according to the standard of ASTMD1652.
5. Resins, epoxy is the Resins, epoxy derived from the compound reaction gained with 4 or 4 above epoxide functional groups shown in compound with 2 epoxy group(ing) shown in the phenolic compound shown in the following formula (I), the formula (II) and the formula (III):
Wherein Z represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
1For identical or different and represent C
1-6Alkyl or hydroxyl; A represents 0 to 4 integer;
Wherein Y represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
2For identical or different and represent C
1-6Alkyl or hydroxyl; B represents 0 to 4 integer;
Wherein A represent chemical bond ,-O-,-S-,-SO
2-,-CO-, C
1-6Stretch alkyl or be selected from the group of following formula:
R
3For identical or different and represent C
1-6Alkyl or hydroxyl; C represents 0 to 2 integer; N is the integer of 0-20;
The scope of ratio [H1/ (E1+E2)] 0.4 to 2.0 of the epoxy equivalent (weight) E2 sum total of the compound shown in the epoxide equivalent E1 of the compound with 2 epoxy group(ing) of the Ahew H1 of the phenolic compound of its Chinese style (I) and formula (II) and the formula (III) with 4 or 4 above epoxide functional groups.
6. Resins, epoxy as claimed in claim 5, it has analyses method with hydrogel permeation layer GPC and measures and to be scaled the weight average molecular weight Mw that polystyrene is counted 3000 to 28000 scopes, and the epoxy equivalent (weight) EEW in 700 to 1500g/eq scopes that measures according to the standard of ASTMD1652.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101175080A CN100453593C (en) | 2005-11-02 | 2005-11-02 | Difficult combustible epoxy resin composition not containing halogen |
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|---|---|---|---|
| CNB2005101175080A CN100453593C (en) | 2005-11-02 | 2005-11-02 | Difficult combustible epoxy resin composition not containing halogen |
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| Publication Number | Publication Date |
|---|---|
| CN1958666A CN1958666A (en) | 2007-05-09 |
| CN100453593C true CN100453593C (en) | 2009-01-21 |
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| CNB2005101175080A Active CN100453593C (en) | 2005-11-02 | 2005-11-02 | Difficult combustible epoxy resin composition not containing halogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090078051A (en) * | 2008-01-14 | 2009-07-17 | 도레이새한 주식회사 | Adhesive composition for halogen-free coverlay film and coverlay film using the same |
| TWI767129B (en) * | 2018-07-11 | 2022-06-11 | 台虹科技股份有限公司 | composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020032279A1 (en) * | 2000-07-19 | 2002-03-14 | Chang Chun Plastics Co., Ltd. | Flame retardant resin and flame retardant composition containing the same |
| JP2003055436A (en) * | 2001-08-17 | 2003-02-26 | Choshun Jinzo Jushisho Kofun Yugenkoshi | Phosphorus-containing resin, and flame-retardant resin composition containing the same |
| US6576690B1 (en) * | 2002-03-22 | 2003-06-10 | Chang Chung Plastics Co., Ltd. | Phosphorous-containing flame retarding epoxy resin and an epoxy resin composition containing the same |
| CN1613910A (en) * | 2003-11-03 | 2005-05-11 | 长春人造树脂厂股份有限公司 | Epoxy composition for light semiconductor packing |
| CN1613911A (en) * | 2003-11-05 | 2005-05-11 | 长春人造树脂厂股份有限公司 | Epoxy composition for light semiconductor packing |
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2005
- 2005-11-02 CN CNB2005101175080A patent/CN100453593C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020032279A1 (en) * | 2000-07-19 | 2002-03-14 | Chang Chun Plastics Co., Ltd. | Flame retardant resin and flame retardant composition containing the same |
| JP2003055436A (en) * | 2001-08-17 | 2003-02-26 | Choshun Jinzo Jushisho Kofun Yugenkoshi | Phosphorus-containing resin, and flame-retardant resin composition containing the same |
| US6576690B1 (en) * | 2002-03-22 | 2003-06-10 | Chang Chung Plastics Co., Ltd. | Phosphorous-containing flame retarding epoxy resin and an epoxy resin composition containing the same |
| CN1613910A (en) * | 2003-11-03 | 2005-05-11 | 长春人造树脂厂股份有限公司 | Epoxy composition for light semiconductor packing |
| CN1613911A (en) * | 2003-11-05 | 2005-05-11 | 长春人造树脂厂股份有限公司 | Epoxy composition for light semiconductor packing |
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| CN1958666A (en) | 2007-05-09 |
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