CN104877134B - Halogen-free flameproof polyimide resin composition and the prepreg made using which and laminate - Google Patents
Halogen-free flameproof polyimide resin composition and the prepreg made using which and laminate Download PDFInfo
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Abstract
The invention discloses a kind of halogen-free flameproof polyimide resin composition, with solid weight meter, including：(a) BMI；B () is combined allyl compound；(c) phosphorus-containing compound；The preparation method of halogen-free flameproof polyimide resin composition：BMI, compound allyl compound and phosphorus-containing compound are taken in reaction bulb, heating response；Compound allyl compound is made up of first kind allyl compound and Equations of The Second Kind allyl compound；First kind allyl compound is selected from one or more in diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, diallyl diphenyl ether；Equations of The Second Kind allyl compound is selected from one or more in diallyl bisphenol diglycidyl ether, diallyl bisphenol-S diglycidyl ether, diallyl diphenyl ether diglycidyl ether.The laminate of the present invention integrates excellent anti-flammability, heat resistance, high tenacity, low water absorption, superior dielectric performance and anti-flammability.
Description
Technical field
The invention belongs to technical field of electronic materials, is related to a kind of halogen-free flameproof polyimide resin composition and uses which
The prepreg and laminate of making.
Background technology
With the development in electronic unit multifunction, high performance, high reliability and environmentally friendly direction, it is necessary to improve sheet material
Heat resistance, to meet Pb-free coating and the multiple harsh processing technology of pressing, the heat resistance of traditional FR-4 materials is far from
Can meet and require.
Bimaleimide resin is the compound that a class has double activated end group, can in the presence of heating or catalyst
With crosslinking curing, with excellent heat resistance, humidity resistance, dielectric properties, good mechanical property and dimensional stability, therefore
It is widely used in Aero-Space, electronic apparatus, friendship as High-performance adhesive, resin matrix for advanced composite materials body, insulated paint etc.
In numerous high-technology fields such as logical transport.But because there is monomer solubility difference and solidfied material fragility in bimaleimide resin
Big the shortcomings of, when being applied to copper-clad plate field, need to be modified which.
At present, conventional method of modifying is which to be changed using aromatic diamines compound or allylic compound
Property, crystalline texture is destroyed by chain extension, dissolubility and toughness etc. is improved.Aromatic diamines compound is anti-by Michael's addition
Should realize being modified BMI, modified product has a certain degree of improvement in terms of dissolubility, toughness；But
That aromatic diamine toxicity is larger, modified product can only be dissolved in high bp polar solvent (such as DMF, NMP etc.), at the same its
Larger room for promotion is still suffered from terms of toughness, caking property.And the modified product of allyl compound toughness, caking property,
Dissolubility (being soluble in low boiling point solvent, such as PM, butanone, acetone etc.) has compared with aromatic diamines compound further to be improved,
It is one of method of current bi-maleimide modified main employing；At present, conventional allylic compound, such as pi-allyl are double
Phenol A, pi-allyl bisphenol S, phenol type pi-allyl phenolic aldehyde, allyl phenol oxygen, aryl allyl alkylphenol etc., however, with these alkene
The modified bimaleimide resin of compound in terms of heat resistance, water absorption rate, dielectric properties, flammability, toughness often
Attend to one thing and lose sight of another.Additionally, the fire-retardant problem of modified product is not resolved.
For the problems referred to above, solve at present fire-retardant problem application it is most be halogen system compound, but halogen system compound conduct
Fire retardant can produce the carcinogens such as bioxin, furans and corrosive gas during burning, to human health and ecology
Environment works the mischief.Therefore, it is many at present that halogenated flame retardant is substituted using phosphonium flame retardant, but as the fire retardant of addition type can pole
The performance of the big low sheet material of sinking and there is the risk of migration precipitation, therefore, the phosphonium flame retardant of response type is studied in recent years
The extensive concern of personnel.For example, one kind is disclosed in Chinese invention patent 201010270929.8 using DOPO and BMI and alkene
The method that compound reaction prepares flame-retarded resin, with preferable flame retardant effect, but the storage stability of its prepolymer and
The toughness of solidfied material still needs to improve.Additionally, a kind of resistance of halogen-free phosphorus-containing is disclosed in Chinese invention patent 201110239153.8
Combustion polyimide resin composition and preparation method thereof, is obtained using one-step method reaction, and the storage for improving resin combination is steady
The toughness of qualitative and solidfied material, but bisphenol A type epoxy resin itself heat resistance of its addition is extremely low, causes the span for obtaining to carry out acyl
The heat resistance of imide resin composition is reduced.
Therefore, the excellent anti-flammability of collection, heat resistance, high tenacity, low water absorption, superior dielectric performance and fire-retardant how to be obtained
Property, in the copper-clad plate material of one, is one of this area technical problem urgently to be resolved hurrily.
The content of the invention
The goal of the invention of the present invention be to provide a kind of halogen-free flameproof polyimide resin composition and made using which half
Cured sheets and laminate.
To achieve the above object of the invention, the technical solution used in the present invention is：A kind of halogen-free flameproof polyimide resin group
Compound, with solid weight meter, including：
(a) BMI：100 parts；
B () is combined allyl compound：40～160 parts；
(c) phosphorus-containing compound：1～75 part；
Wherein, the compound allyl compound is by first kind allyl compound and Equations of The Second Kind allyl compound group
Into, and the mass ratio of first kind allyl compound and Equations of The Second Kind allyl compound is 0～99:1～100；
The first kind allyl compound selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin,
One or more in diallyl diphenyl ether；
The Equations of The Second Kind allyl compound contracts selected from diallyl bisphenol diglycidyl ether, diallyl bisphenol S two
One or more in water glycerin ether, diallyl diphenyl ether diglycidyl ether.
Above, the preparation method of above-mentioned halogen-free flameproof polyimide resin composition is as follows：Take BMI, answer
Allyl compound and phosphorus-containing compound are closed in reaction bulb, heating response, you can obtain the halogen-free flameproof polyimides tree
Oil/fat composition.
Preferably, BMI, compound allyl compound and phosphorus-containing compound are taken in reaction bulb, is heated to
120～160 DEG C, react 10～150min, you can obtain the halogen-free flameproof polyimide resin composition.
The chemical structural formula of the diallyl bisphenol diglycidyl ether is：
The chemical structural formula of the diallyl bisphenol-S diglycidyl ether is：
The chemical structural formula of the diallyl diphenyl ether diglycidyl ether is：
Inorganic filler can also be contained in the resin combination.The inorganic filler is titanium dioxide selected from inorganic filler
One kind in silicon, aluminium hydroxide, Bao Mushi, magnesium hydroxide, talcum, kaolin, aluminum oxide, Firebrake ZB, polytetrafluorethylepowder powder
Or it is several.The silica can be spherical, crystal type or fusion.Preferably, inorganic filler is to be entered with silane coupler
The surface-treated inorganic filler of row.The preferred end group of the silane coupler contains double bond or epoxide group.By above-mentioned coupling agent
When the inorganic filler being surface-treated is added to resin combination, because of double bond/epoxide group and the modified span of coupling agent
Imide prepolymer has excellent com-patibilising effect so that the viscosity of overall resin combination rises slowly, and filler is in resin group
Dispersiveness in compound preferably, is efficiently solved because viscosity is big and the unmanageable problem of reaction between resin Composition, is improved
The surface smoothness of prepreg.
Phosphorus content in the halogen-free flameproof polyimide resin composition accounts for polyimide resin composition gross weight
0.5～2.5%.Additionally, research finds：It is when system phosphorus content is too low, fire-retardant not reach V-0 ranks；And work as system phosphorus content
When too high, heat resistance (Tg, Td and T300 etc.) can be caused to decline, water absorption rate rises.
The Equations of The Second Kind allyl compound that the present invention is adopted contains epoxide group, improves modified bismaleimide pre-polymerization
The dissolubility and storage stability of thing, the pi-allyl in its structure can be polymerized with the double bond in BMI, draw
The epoxide group for entering can carry out ring-opening reaction, the epoxide group of residual with the active group in phosphorus-containing compound (P-H or N-H)
As active end group occur when further heating autohemagglutination or with formula in other resin Composition copolymerization, epoxide group draws
Enter to improve the crosslink density of solidfied material；Simultaneously as a large amount of ehter bonds formed after epoxide group open loop, improve solidfied material
Toughness.
In above-mentioned technical proposal, the BMI is selected from 4,4 '-diphenyl methane dimaleimide, 4,4 '-two
One kind in phenylate BMI, 4,4 '-hexichol isopropyl BMI, 4,4 '-diphenyl sulphone (DPS) BMI
Or it is several.
Preferably, the mass ratio of the first kind allyl compound and Equations of The Second Kind allyl compound is 20～60:40
～80.
In above-mentioned technical proposal, the phosphorus-containing compound selected from phosphorus-containing compound A, phosphorus-containing compound B, phosphorus-containing compound C,
One or more in phosphorus-containing compound D, phosphorus-containing compound E；
The chemical formula of the phosphorus-containing compound A is：
The chemical formula of the phosphorus-containing compound B is：
The chemical formula of the phosphorus-containing compound C is：
The chemical formula of the phosphorus-containing compound D is：
The chemical formula of the phosphorus-containing compound E is：
The present invention is claimed a kind of prepreg made using above-mentioned resin combination simultaneously, by above-mentioned resin combination
Glue is made in the dissolving of thing solvent, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material baking, i.e.,
The prepreg is obtained.
Described solvent selected from acetone, butanone, methylisobutylketone, N, dinethylformamide, N, N- dimethyl acetamide,
One or more in EGME, propylene glycol monomethyl ether.
The reinforcing material can adopt glass-fiber-fabric, such as D glass-fiber-fabrics, E glass-fiber-fabrics, NE glass-fiber-fabrics, S glass-fiber-fabrics and T glasses
Cloth.Here the thickness of glass-fiber-fabric is not particularly limited, but for the laminate of production 0.03～0.20mm of thickness, is generally used
Fibrillation cloth, flat fabric.Additionally, the interface cohesion in order to improve resin and glass-fiber-fabric, glass-fiber-fabric is typically necessary carries out chemical place
Reason, main method is coupling agent treatment, coupling agent used such as epoxy silane, amino silane, vinyl silanes etc..
The prepreg is temperature at 100～200 DEG C, and the time is to dry to be prepared under 1～10min.
The present invention is claimed a kind of laminate made using above-mentioned resin combination simultaneously, at one by above-mentioned
The single or double of prepreg is covered with metal forming, or by least 2 by above-mentioned prepreg superposition after, in its one side or
It is two-sided to be covered with metal forming, suppress 2～4 hours at a temperature of 0.2～2MPa pressure and 180～250 DEG C, you can obtain the lamination
Plate.
The quantity of the prepreg be according to the laminate thickness of customer requirement determining, can be with one or more.Institute
Metal forming is stated, can be Copper Foil, or aluminium foil, thickness is not particularly limited.
As above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. the present invention is using the compound pi-allyl being made up of first kind allyl compound and Equations of The Second Kind allyl compound
Modifying agent of the compound as bimaleimide resin, reacts the Bismaleimide prepolymer for obtaining and has higher reaction
Activity, good dissolubility and storage stability, good toughness after solidification, peel strength is high, water absorption rate is low, dielectric constant is low and protects
The excellent heat resistance of BMI is held, the excellent anti-flammability of the laminate collection for obtaining, heat resistance, high tenacity, low water suction
Rate, superior dielectric performance and anti-flammability can meet the requirement of high-precision electronic baseplate material in one；With energetically reality
Meaning；
2. the halogen-free flameproof polyimide resin composition storage stability of the present invention is good, and reactivity is high, using its system
Achievable Halogen V-0 is fire-retardant for the copper-clad plate of work, with good toughness and peel strength, maintains BMI excellent
Different heat resistance, achieves significant effect, can be applicable to the fields such as anti-aging high temperature resistant, integrated antenna package, high-speed high frequency,
Have broad application prospects.
Specific embodiment
The present invention is further described with reference to embodiment.
Embodiment one：
Take 4,4 '-diphenyl methane dimaleimide 100g, diallyl bisphenol diglycidyl ether 70g (epoxide equivalents
256g/eq), phosphorus-containing compound (A) 20g is put in 500mL reaction bulbs, is slowly heated to 120～160 DEG C using oil bath and is kept
30min being reacted under stirring condition, obtaining the polyimide resin composition of halogen-free flameproof, room temperature is cooled to after the completion of reaction.
Embodiment two：
Take 4,4 '-Diphenyl Ether Bismaleimide 30g, 4,4 '-diphenyl methane dimaleimide 90g, diallyl are double
Phenol A 40g, diallyl bisphenol diglycidyl ether 20g (epoxide equivalent 220g/eq), phosphorus-containing compound (A) 23g are put into
In 500mL reaction bulbs, 120～160 DEG C are slowly heated to using oil bath and react 50min under the conditions of being kept stirring for, obtain Halogen
Fire-retardant polyimide resin composition, is cooled to room temperature after the completion of reaction.
Embodiment three：
4 are taken, 4 '-Diphenyl Ether Bismaleimide 125g, allyl phenoxy resin 20g, diallyl bisphenol two shrink sweet
Oily ether 50g (epoxide equivalent 215g/eq), phosphorus-containing compound (B) 30g are put in 500mL reaction bulbs, are slowly heated to using oil bath
120～160 DEG C and 60min being reacted under the conditions of being kept stirring for, obtaining the polyimide resin composition of halogen-free flameproof, reaction is completed
After be cooled to room temperature.
Example IV：
4 are taken, 4 '-hexichol isopropyl BMI 100g, allyl phenol urea formaldehyde 30g, diallyl bisphenol two contract
Water glycerin ether 30g (epoxide equivalent 250g/eq), phosphorus-containing compound (C) 7g are put in 500mL reaction bulbs, are slowly added using oil bath
Heat reacts 45min to 130～150 DEG C and under the conditions of being kept stirring for, and obtains the polyimide resin composition of halogen-free flameproof, reacts
After the completion of be cooled to room temperature.
Embodiment five：
4 are taken, 4 '-diphenyl sulphone (DPS) BMI 110g, diallyl bisphenol S 10g, diallyl bisphenol two shrink sweet
Oily ether 70g (epoxide equivalent 225g/eq), phosphorus-containing compound (E) 21g are put in 500mL reaction bulbs, are slowly heated to using oil bath
130～150 DEG C and 30min being reacted under the conditions of being kept stirring for, obtaining the polyimide resin composition of halogen-free flameproof, reaction is completed
After be cooled to room temperature.
Comparative example one：
4 are taken, 4 '-diphenyl methane dimaleimide 100g, pi-allyl bisphenol-A 70g, phosphorus-containing compound (A) 20g are put into
In 500mL reaction bulbs, 130～150 DEG C are slowly heated to using oil bath and react 50min under the conditions of being kept stirring for, be modified
Bismaleimide resin, is cooled to room temperature after the completion of reaction.
Comparative example two：
Take 4,4 '-diphenyl methane dimaleimide 150g, pi-allyl bisphenol-A 100g, bisphenol A type epoxy resin 15g,
Ring-type phenoxy phosphazene compound 33g (Fushimi Pharmaceutical Co., Ltd, FP-100), is put into 500mL reactions
In bottle, 130～150 DEG C are slowly heated to using oil bath and reaction obtains modified quartz sand in 3 hours under the conditions of being kept stirring for, instead
Room temperature is cooled to after the completion of answering.
Comparative example three：
Take 4,4 '-diphenyl methane dimaleimide 100g, pi-allyl phenolic aldehyde diglycidyl ether 70g (epoxide equivalents
250g/eq), phosphorus-containing compound (A) 20g, is put in 500mL reaction bulbs, is slowly heated to 130～150 DEG C using oil bath and protects
Hold reaction under stirring condition and obtain modified quartz sand in 3 hours, after the completion of reaction, be cooled to room temperature.
First, prepreg makes：
The resin combination of the preparation of 100g above-described embodiments one to five is taken, proper amount of acetone dissolving is added, after stirring
To glue.300 × 450mm, smooth bright and clean 7628E- glass-fiber-fabrics are chosen, above-mentioned glue is uniformly coated, in an oven at 165 DEG C
Baking 5min is obtained a series of 5 groups of prepregs.
One to three gained modified quartz sand of comparative example prepares prepreg method ibid.
2nd, copper-clad plate makes：
Above-mentioned gained prepreg is taken, each group takes 8, by the semi-solid preparation superposition of 8 sanction burr removings, enclose 35 up and down micro-
The Copper Foil of rice, is placed in compacting in hot press and obtains 7 groups of copper-clad plates.Wherein, using staged (substep heats up and boosts) program pressure
System, specially：Temperature, 15min rise to 150 DEG C from room temperature and keep 30min, and then 5min is raised to 180 DEG C of holding 2hr, finally
10min is raised to 230 DEG C of holding 2.0hr；30min；Pressure, 1min rise to 0.6Mpa pressurize 30min, and then 1min rises to 1.0Mpa
Pressurize 1hr, last 1min rise to 2Mpa pressurize 3.0hr57min；Post-treatment condition：220℃/4hr.
Performance test is carried out according to copper-clad plate of the prior art to 8 groups of embodiments of above-mentioned gained and comparative example, be the results are shown in Table
1。
1 embodiment of table and the key property of copper-clad plate prepared by comparative example
Partial test method of the present invention is specific as follows：
Humidity resistance：Using pressure cooker gluten substitute, sheet material is through 121 DEG C of continuously cookings 180 of pressure cooker (0.105MPA)
After minute, observation layering, bubble time in 288 DEG C of scolding tin of immersion；
Impact flexibility：Using 5512 Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.If sheet material impacts
Cross pattern afterwards is clear and elongated, illustrates that the toughness of sheet material is better；Conversely, cross pattern is obscured or no cross pattern, sheet material is illustrated
Poor toughness, fragility is big, particularly may be divided into it is excellent, good, in, differ from four grades；
Storage stability：Resin combination is dissolved in acetone solvent by solids content 55%, after sealing, one week is stood,
Resin layering seen whether, separated out.
From table 1 it follows that compared with comparative example one, resin combination obtained by the present invention has storage stability
Good toughness, peel strength height and the low advantage of water absorption rate after good, solidification.
Compared with documents two, obtained by the present invention, sheet material has more excellent heat resistance (Tg, Td and T300).
Compared with documents three (individually adopting pi-allyl novolac glycidyl ethers), obtained by the present invention, sheet material has solid
After change, good toughness, water absorption rate be low and the low advantage of dielectric constant.Mainly caused by two aspects with the difference of documents three：It is first
First, as the rigid radical density in phenolic resin main framing structure is larger and without rotatable group, causes its solidfied material toughness
It is poor；On the other hand, pi-allyl phenolic aldehyde during etherificate due to steric effect, the hydroxyl in the middle of molecule not completely etherificate and
Reaction is difficult, is caused remaining hydroxyl groups in solidfied material, and hydroxyl is belonged to polar group, easily caused solidfied material water absorption rate greatly and dielectric is normal
Number is higher.
In sum, obtained by the present invention it is the excellent anti-flammability of laminate collection, heat resistance, high tenacity, low water absorption, excellent
Different dielectric properties and anti-flammability can be applicable to the fields such as anti-aging high temperature resistant, integrated antenna package, high-speed high frequency in one.
Above example, not imposes any restrictions to the content of the composition of the present invention, every technology according to the present invention
Any trickle amendment, equivalent variations and modification that essence or composition composition or content are made to above example, still fall within
In the range of technical solution of the present invention.
Claims (5)
1. a kind of halogen-free flameproof polyimide resin composition, it is characterised in that with solid weight meter, including：
(a) BMI：100 parts；
B () is combined allyl compound：40～160 parts；
(c) phosphorus-containing compound：1～75 part；
Wherein, the compound allyl compound is made up of first kind allyl compound and Equations of The Second Kind allyl compound, and
The mass ratio of first kind allyl compound and Equations of The Second Kind allyl compound is 20～60:40～80；
The first kind allyl compound is selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, diene
One or more in propyl group diphenyl ether；
The Equations of The Second Kind allyl compound shrinks sweet selected from diallyl bisphenol diglycidyl ether, diallyl bisphenol S two
One or more in oily ether, diallyl diphenyl ether diglycidyl ether；
The phosphorus-containing compound selected from phosphorus-containing compound A, phosphorus-containing compound B, phosphorus-containing compound C, phosphorus-containing compound D, containing phosphatization
One or more in compound E；
The chemical formula of the phosphorus-containing compound A is：
The chemical formula of the phosphorus-containing compound B is：
The chemical formula of the phosphorus-containing compound C is：
The chemical formula of the phosphorus-containing compound D is：
The chemical formula of the phosphorus-containing compound E is：
2. resin combination according to claim 1, it is characterised in that：The BMI is selected from 4,4 '-hexichol
Methane BMI, 4,4 '-Diphenyl Ether Bismaleimide, 4,4 '-hexichol isopropyl BMI, 4,4 '-two
One or more in benzene sulfone BMI.
3. resin combination according to claim 1, it is characterised in that：The content of the compound allyl compound is 60
～120 parts.
4. it is a kind of using resin combination as claimed in claim 1 make prepreg, it is characterised in that：By claim
Glue is made in resin combination solvent dissolving described in 1, and then reinforcing material is immersed in above-mentioned glue；To increase after dipping
After strong material baking, you can obtain the prepreg.
5. it is a kind of using resin combination as claimed in claim 1 make laminate, it is characterised in that：At one by right
It is required that the single or double of the prepreg described in 4 is covered with metal forming, or it is solid by half described in claim 4 by least 2
After changing piece superposition, metal forming is covered with its single or double, 2～4 are suppressed at a temperature of 0.2～2MPa pressure and 180～250 DEG C
Hour, you can obtain the laminate.
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| JP6761572B2 (en) * | 2015-11-11 | 2020-09-30 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board |
| JP6618036B2 (en) * | 2015-11-25 | 2019-12-11 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board |
| KR20190035731A (en) * | 2016-08-05 | 2019-04-03 | 닛뽄 가야쿠 가부시키가이샤 | Maleimide resin composition, prepreg, cured product thereof, and semiconductor device |
| CN109306040A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
| CN109306044A (en) * | 2017-07-26 | 2019-02-05 | 郑州大学 | A kind of intrinsic flame-retarded resin of low polarity and its preparation method and application |
| CN109535628B (en) * | 2018-11-28 | 2020-11-24 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same |
| CN109929109A (en) * | 2019-03-19 | 2019-06-25 | 武汉理工大学 | A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof |
| CN115873251A (en) * | 2022-12-27 | 2023-03-31 | 苏州生益科技有限公司 | Modified maleimide prepolymer, preparation method thereof and resin composition |
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| WO2000071614A1 (en) * | 1999-05-21 | 2000-11-30 | Miguel Albert Capote | High performance cyanate-bismaleimide-epoxy resin compositions for printed circuits and encapsulants |
| CN101974156B (en) * | 2010-09-03 | 2011-12-28 | 苏州生益科技有限公司 | Halogen-free flam retardant prepolymer, preparation method thereof and application of halogen-free flam retardant prepolymer in copper clad laminate (CCL) |
| CN102276837B (en) * | 2011-08-19 | 2013-01-02 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
| CN103524739A (en) * | 2013-10-09 | 2014-01-22 | 胶州市精细化工有限公司 | Allyl/epoxy etherified phenolic aldehyde modified bismaleimide resin and preparation method thereof |
| JP6348700B2 (en) * | 2013-11-01 | 2018-06-27 | 京セラ株式会社 | Thermosetting resin composition for semiconductor bonding and semiconductor device using the same |
| CN104194269B (en) * | 2014-08-31 | 2016-04-20 | 海安南京大学高新技术研究院 | Reversible repairing effect mold base resin of a kind of pultrusion and preparation method thereof |
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