Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, and a kind of composition epoxy resin not halogen-containing and antimony element and that can satisfy the environmental protection of lead-free process is provided.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of composition epoxy resin, it comprises Resins, epoxy, solidifying agent resol, curing catalyst, compound inorganic stuffing, releasing agent, coupling agent and tinting material, be characterized in that described Resins, epoxy is that general formula is (I) and the mixture of general formula for the Resins, epoxy of (II)
Wherein n is 0~100 integer.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that described general formula is the 1-28% that the Resins, epoxy of (II) accounts for the Resins, epoxy total amount, preferred 16-28%, preferred again 21-25%.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that the equivalence ratio of described solidifying agent resol and Resins, epoxy is 0.6-1.6, preferred 0.8-1.4.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that described compound inorganic stuffing is 80~90% of a composition total weight.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that described compound inorganic stuffing is the mixture of A, two kinds of different-grain diameter silica flours of B, wherein the meta particle diameter d50 of A part is 16-22um, the meta particle diameter d50 of B part is 0.5-1.5um.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described one sharp composition epoxy resin, be characterized in that wherein A partly accounts for 90~98% of compound inorganic stuffing total amount per-cent, B partly accounts for 2~10% of total amount per-cent.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that it can also contain fire retardant, described fire retardant is for containing phosphorus type flame retardant and metal hydroxides based flame retardant.
Technical problem to be solved by this invention can also further realize by following technical scheme.With described a kind of composition epoxy resin, be characterized in that it can also contain property-modifying additive, described property-modifying additive is absorption of stress agent, bonding agent and ion capturing agent.
Can not satisfy the many-sided performance requirement of environmental protection at present, particularly Halogen not not contained antimony and can satisfy the critical problem of the requirement of lead-free solder process high-temperature reliability composition epoxy resin.The present invention is by optimum combination Resins, epoxy, the kind and the proportioning of further preferred consolidation agent resol, and adopt high filling technique, a kind of composition epoxy resin of halogen-free stibium-free is provided, this composition epoxy resin has characteristics such as good flowability, flame retardant resistance and low water absorbable, the fire-retardant quality standard of UL-94V-0 level can not only be reached, and the high temperature reliability requirement of the lead-free solder technology of environmental protection can also be satisfied.
The present invention is a kind of composition epoxy resin of halogen-free stibium-free antiflaming agent, by preferred epoxy and solidifying agent resol, and optimization proportioning, make preferred epoxy resin composition and reactive modified phenolic resin form a kind of composition epoxy resin from flame-out network structure, promptly when composition epoxy resin burns, can form a kind of foam layer (fire-retardant barrier), obstruct oxygen passes through, and cutting off heat passage reaching from flame-out effect, the resin compound after solidifying simultaneously forms in main chain contains the polyaromatic group, network with heat resistanceheat resistant decomposition reaction plays important effect to the stability of foam layer.This composition has the performance of good heat-resisting scolder and thermal cycling, and by high filling technique, filling ratio was at 80~90% o'clock, and this composition still has good flowability, also have very low water-absorbent, can satisfy the high temperature reliability requirement of lead-free solder technology.
Composition epoxy resin of the present invention can be by making with 70~100 ℃ of mixing postcooling pulverizing on twin-screw extruder.This green composition epoxy resin can not only reach the flame-retardant standard of UL-94V-0 level, and meet and satisfy environmental protection to the halogen-free stibium-free of composition epoxy resin and can satisfy the requirement of lead-free process high temperature reliability, be a kind of outstanding epoxy resin composition for semiconductor encapsulation.Composition epoxy resin of the present invention is applicable to green encapsulation semiconductor device and unicircuit.
Embodiment
Embodiment 1.A kind of composition epoxy resin, it comprises Resins, epoxy, solidifying agent resol, curing catalyst, compound inorganic stuffing, releasing agent, coupling agent and tinting material, described Resins, epoxy is that general formula is (I) and the mixture of general formula for the Resins, epoxy of (II),
Wherein n is 0~100 integer.
Embodiment 2.In the embodiment 1 described composition epoxy resin, general formula accounts for 20% of Resins, epoxy total amount for the Resins, epoxy of (II).
Embodiment 3.In the embodiment 1 described composition epoxy resin, general formula accounts for 1% of Resins, epoxy total amount for the Resins, epoxy of (II).
Embodiment 4.In the embodiment 1 described composition epoxy resin, general formula accounts for 28% of Resins, epoxy total amount for the Resins, epoxy of (II).
Embodiment 5.In the embodiment 1 described composition epoxy resin, general formula accounts for 16% of Resins, epoxy total amount for the Resins, epoxy of (II), and the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 1.4.
Embodiment 6.In the embodiment 1 described composition epoxy resin, general formula accounts for 19% of Resins, epoxy total amount for the Resins, epoxy of (II), and the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 1.0.
Embodiment 7.In the embodiment 1 described composition epoxy resin, general formula accounts for 21% of Resins, epoxy total amount for the Resins, epoxy of (II), and the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 1.2, and described compound inorganic stuffing is 85% of a composition total weight.
Embodiment 8.In the embodiment 1 described composition epoxy resin, general formula accounts for 10% of Resins, epoxy total amount for the Resins, epoxy of (II), and the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 0.8, and described compound inorganic stuffing is 80% of a composition total weight.
Embodiment 9.In the embodiment 1 described composition epoxy resin, general formula accounts for 25% of Resins, epoxy total amount for the Resins, epoxy of (II), the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 1.3, described compound inorganic stuffing is 87% of a composition total weight, described compound inorganic stuffing is the mixture of A, two kinds of different-grain diameter silica flours of B, wherein the meta particle diameter d50 of A part is 18um, the meta particle diameter d50 of B part is 1.0um, A partly accounts for 96% of compound inorganic stuffing total amount per-cent, and B partly accounts for 4% of total amount per-cent.
Embodiment 10.In the embodiment 1 described composition epoxy resin, general formula accounts for 5% of Resins, epoxy total amount for the Resins, epoxy of (II), the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 1.1, described compound inorganic stuffing is 88% of a composition total weight, described compound inorganic stuffing is the mixture of A, two kinds of different-grain diameter silica flours of B, wherein the meta particle diameter d50 of A part is 16um, the meta particle diameter d50 of B part is 1.5um, A partly accounts for 90% of compound inorganic stuffing total amount per-cent, and B partly accounts for 10% of total amount per-cent.
Embodiment 11.In the embodiment 1 described composition epoxy resin, general formula accounts for 15% of Resins, epoxy total amount for the Resins, epoxy of (II), the equivalence ratio of solidifying agent resol and Resins, epoxy is preferred 0.8, described compound inorganic stuffing is 82% of a composition total weight, described compound inorganic stuffing is the mixture of A, two kinds of different-grain diameter silica flours of B, wherein the meta particle diameter d50 of A part is 22um, the meta particle diameter d50 of B part is 0.5um, A partly accounts for 95% of compound inorganic stuffing total amount per-cent, and B partly accounts for 5% of total amount per-cent.
Embodiment 12.In the embodiment 1 described composition epoxy resin, it also contains fire retardant, and described fire retardant is to contain a kind of in phosphorus type flame retardant or the metal hydroxides based flame retardant.
Embodiment 13.In the embodiment 1 described composition epoxy resin, it also contains property-modifying additive, and described property-modifying additive is absorption of stress agent, bonding agent and ion capturing agent.
Embodiment 14.Select Resins, epoxy for use: 50 grams, its formula of (II) account for 10.5 grams, and general formula (I) accounts for 39.5 grams; Resol: 43 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 561 grams, B part 23 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.During preparation, above-mentioned starting material are pulverized with 90 ℃ of mixing postcooling on twin-screw extruder.
Embodiment 15.Select Resins, epoxy for use: 50 grams, its formula of (II) account for 10.5 grams, and general formula (I) accounts for 39.5 grams; Resol: 47 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 582 grams, B part 24 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 70 ℃ of mixing postcooling on twin-screw extruder.
Embodiment 16.Select Resins, epoxy for use: 50 grams, its formula of (II) account for 10.5 grams, and general formula (I) accounts for 39.5 grams; Resol: 51 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 604 grams, B part 25 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 80 ℃ of mixing postcooling on twin-screw extruder.
Embodiment 17.Select Resins, epoxy for use: 50 grams, its formula of (II) account for 10.5 grams, and general formula (I) accounts for 39.5 grams; Resol: 60 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part (653 gram), B part (27 gram); Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 100 ℃ of mixing postcooling on twin-screw extruder.
Embodiment 18.Be the contrast experiment that the contriver did below.
The main performance index of choosing the prepared Resins, epoxy of embodiment 14,15,16,17 and following reference examples 1,2,3,4 compares as follows,
Reference examples 1.Select general formula (I) Resins, epoxy for use: 50 grams; Resol: 37 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 528 grams, B part 22 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 80 ℃ of mixing postcooling on twin-screw extruder.
Reference examples 2.Select general formula (I) Resins, epoxy for use: 50 grams; Resol: 41 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 549 grams, B part 23 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 90 ℃ of mixing postcooling on twin-screw extruder.
Reference examples 3.Select general formula (I) Resins, epoxy for use: 50 grams; Resol: 44 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 565 grams, B part 24 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 70 ℃ of mixing postcooling on twin-screw extruder.
Reference examples 4.Select general formula (I) Resins, epoxy for use: 50 grams; Resol: 52 grams; Phosphorous curing catalyst/tertiary amines curing catalyst: 1.0/0.8 gram; Compound inorganic stuffing: A part 610 grams, B part 25 grams; Carbon black: 3 grams; Carnauba wax: 3 grams; Coupling agent: 5mL.Above-mentioned starting material are pulverized with 100 ℃ of mixing postcooling on twin-screw extruder.
Main performance index is tested with following method among the contrast experiment:
1, flame retardant resistance: sample is made the sample piece of 1/16 inch thickness under 175 ℃/25Mpa condition, under the condition of 175 ℃/6h, carry out after fixing then, carry out flame retardant test by the vertical combustion method according to GB4609-84 at last.
2, water-absorbent: sample is made the disk of 00 * 2 (mm), and carry out after fixing under the condition of 100 ℃/24h, then according to GB1034-86 successively: oven dry-drying-weighing m1-boil-sassafras does surface-weighing m2.The calculating of water-intake rate: Wp=(m2-m1)/m1 * 100%,
3, viscosity: the CFT heightization instrument that flows, sample is made 00 * 2g, under 150 ℃/10kg condition, test obtaining.
4, filling: ultrasonic scanning SAT method observation.
Experimental result is as follows:
The main performance index table of embodiment
Project | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 |
Resins, epoxy | ????50 | ????50 | ????50 | ????50 |
Resol | ????43 | ????47 | ????51 | ????60 |
Phosphorous/the tertiary amines curing catalyst | ????1.0/0.8 | ????1.0/0.8 | ????1.0/0.8 | ????1.0/0.8 |
Compounded mix | The A part | ????561 | ????582 | ????604 | ????653 |
The B part | ????23 | ????24 | ????25 | ????27 |
Carbon black | ????3 | ????3 | ????3 | ????3 |
Carnauba wax | ????3 | ????3 | ????3 | ????3 |
Coupling agent | ????5 | ????5 | ????5 | ????5 |
Properties-correcting agent | ????4 | ????4 | ????4 | ????4 |
Index parameter | Flame retardant resistance | ????V-0 | ????V-0 | ????V-0 | ????V-0 |
Water-intake rate | ????0.10 | ????0.14 | ????0.19 | ????0.20 |
Viscosity | ????48.9 | ????50.8 | ????60.5 | ????57.0 |
Filling | Well | Well | Well | Well |
The main performance index table of reference examples
Project | Reference examples 1 | Reference examples 2 | Reference examples 3 | Reference examples 4 |
Resins, epoxy | ????50 | ????50 | ????50 | ????50 |
Resol | ????37 | ????41 | ????44 | ????52 |
Phosphorous/the tertiary amines curing catalyst | ????1.0/0.8 | ????1.0/0.8 | ????1.0/0.8 | ????1.0/0.8 |
Compounded mix | The A part | ????528 | ????549 | ????565 | ????61?0 |
The B part | ????22 | ????23 | ????24 | ????25 |
Carbon black | ????3 | ????3 | ????3 | ????3 |
Carnauba wax | ????3 | ????3 | ????3 | ????3 |
Coupling agent |
????5 |
????5 |
????5 |
????5 |
Properties-correcting agent |
????4 |
????4 |
????4 |
????4 |
Index parameter |
Flame retardant resistance |
????V-1 |
????V-1 |
????V-1 |
????V-0 |
Water-intake rate |
????0.20 |
????0.34 |
????0.40 |
????0.55 |
Viscosity |
????58.7 |
????140.3 |
????182.0 |
????163.9 |
Filling |
Well |
Well |
The cavity |
The cavity |