CN1710195A - Paper-base composite material for preparing honeycomb briquette core material and its preparing method - Google Patents
Paper-base composite material for preparing honeycomb briquette core material and its preparing method Download PDFInfo
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Abstract
The invention relates to a production technique of paper-base complex material for honeycomb core material preparation, includes following steps: 1, crush with beater the fiber of 30 to 95 weight percent and adherent of 5 to 70 weight percent, then add in dispersant producing cream with density of fiber and adherent at 0.001 - 0.05 percent, and dispersant at 0 - 1 weight percent; 2, shape by heat pressing acquiring paper-base complex material of strong stretching resistance, tearing resistance, layer baring resistance and abrading resistance.
Description
Technical field
The present invention relates to paper technology, specifically is to be used to paper substrate composite for preparing comb core and preparation method thereof.
Background technology
Cellular material is because the mechanical property of lightweight, brilliance is widely used on the inferior stressed structure member of big rigidity of space flight and aviation, car and boat, building materials.The paper base material of traditional preparation process comb core usually uses string or common synthetic fiber, and the Young's modulus of the paper base material that is made by these fibers is relatively low, therefore traditional cellular machinery performance all relatively a little less than.And fire-retardant, high temperature resistant, the hypotoxicity of these materials, smog, protection against the tide and electric property are all poor, have therefore influenced the performance of whole cellular material, can only be with comparing low-grade structural material.
High performance fiber is used for the making of cellular material, can give the characteristic of material high-strength and high-modulus, can also give material fire prevention, anticorrosion, sound insulation, thermal insulation and outstanding electric property.The patent No. is that 93106746.4 Chinese invention patent discloses a kind of method for preparing the powerful aramid paper of high-air-permeability, and this preparation method adopts 45～97% Fanglun 1414,3～30% polyisophthaloyl metaphenylene diamide pulp, 0～35% quartz fibre to prepare a kind of aramid fiber paper; The patent No. is the preparation method that 97102466.9 Chinese invention patent discloses a kind of all-aromatic polyamide fiber sheet, and this polyamide fiber sheet comprises PPTA staple fibre and 4～30% parts by weight of adhesive of 70～90 weight portions by the poly staple fibre and 70～95% (weight) of 5～30% (weight); The patent No. is that 99125156.3 Chinese invention patent discloses-preparation method of kind of completely aromatic-polyamide-fiber synthesized paper sheet, and this synthesized paper sheet contains the aramid fiber short fibre (containing 30% weight or higher PPTA staple fibre) of 70～96% weight and the adhesive of 4～30% weight; The patent No. is the laminated plate material preparation method that 00810718.1 Chinese invention patent discloses a kind of Wholly aromatic polyamide paper and made from it, and the poly-clarified butter amine paper of this full aromatics adopts 60～97% Fanglun 1414 and 3～40% polyisophthaloyl metaphenylene diamide pulp to make.Above patent all is just to adopt Fanglun 1414 and polyisophthaloyl metaphenylene diamide pulp manufacturing to be specifically designed to the aramid fiber paper of substrate for printed circuit board.These aramid fiber paper have good DIMENSIONAL STABILITY and insulating properties under hot and humid degree, but because mechanical performance and dielectric properties are relatively poor, are not suitable for preparing the cellular material that is used as the saturating ripple of high power high frequency.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of preparation method who is used to prepare the paper substrate composite of comb core, the paper substrate composite that is used to prepare comb core that obtains having mechanical performance and dielectric properties excellence.
Another object of the present invention is to provide the paper substrate composite of described method preparation.
The preparation method who is used to prepare the paper substrate composite of comb core of the present invention comprises the steps:
(1) 30～95 parts by mass fibers and 5～70 parts by mass adhesives are broken up with beater, added dispersant, making fiber and binder concn is 0.001～0.05% water slurry, and the concentration of dispersant in water slurry is 0～1% quality;
(2) the papermaking wet moulding dehydrates;
(3) hot-forming;
Described fiber is inorfil and/or synthetic fiber;
Described adhesive is that thermosetting resin, thermoplastic resin fibre or fibrid are or/and fine strip body.
Described dispersant is one or more the mixture in surfactant, water-soluble high-molecular compound, acid and/or the inorganic salts.
Described inorfil is one or more in glass fibre, quartz fibre, the ceramic fibre; Described synthetic fiber are one or more among polyamide fiber, polyparaphenylene Ben Bing Er oxazole fiber, Fanglun 1313, the Fanglun 1414.
Described thermosetting resin is epoxy resin, phenolic resins, melamine resin, isocyanate resin or polyimide resin; Described thermoplastic resin fibre is polyesters staple fibre or polyamide-based fiber; Described fibrid is polyamide, polyester or poly fibrid; Described fine strip body is PPTA or polyparaphenylene Ben Bing Er oxazole fine strip body.
Described dispersing aid is wherein one or more of surfactant, water-soluble high-molecular compound, acid, inorganic salts.
Described surfactant is quaternary amine, soap, Sulfonates or polyethylene glycol oxide; Described water-soluble high-molecular compound is polyacrylic acid or its copolymer analog, polyvinyl alcohol or derivatives thereof class, natural polymer derivatives class; Described acid comprises hydrochloric acid or sulfuric acid.Described inorganic salts are sodium phosphate etc. for example.
Step (2) can adopt the general forming method of papermaking, and the preferred tiltedly net former of the present invention carries out wet moulding.
It is hot-forming that step (3) can adopt the papermaking current techique to carry out; The preferred roller mill of the present invention is 150～360 ℃ of temperature, and 20～400Kg/cm linear pressure is following or use flat-bed press 180～320 ℃ of temperature, carries out hot-forming under 15～25MPa pressure.
Principle of the present invention: provide and use various fiber to prepare lightweight, high-strength paper substrate composite, this paper base material is suitable for making comb core.Because under microwave condition, microwave produces electric field, electronics in the material and dipole also will change the variation of their orientation with the response electric field fast, microwave frequency is high more, power is big more, the quick reorientation of electronics and the induction fast rotational of permanent dipole will cause the rising of material internal temperature, particularly generate heat after to a certain degree, and material can scaling loss.And the dielectric constant of material is low more, and the signal transmitting speed is just fast more, loss is also more little.Therefore usually the selected introductions electric constant is less for electromagnetic wave transparent material.The fiber that meets this machinery and dielectric properties can be an inorfil, also can be the organic polymer fiber.Inorfil comprises glass fibre, quartz fibre and ceramic fibre; Organic fiber comprises polyamide fiber, polyparaphenylene Ben Bing Er oxazole fiber, Fanglun 1313, Fanglun 1414 and other aramid fiber fibrids.This fibre length is 2～20mm, preferred 4～12mm.The paper base material intertwined point that too short fiber makes is few, and intensity, modulus are relatively poor, and oversize fiber is difficult to disperse, and the intensity of paper base material is also relatively poor.
Preferably between 5～70 parts by mass, when the addition of adhesive was lower than 5 parts by mass, interfibrous viscous force died down the addition of adhesive, and the intensity that shows as paper base material sharply descends; If the content of adhesive is higher than 70 parts by mass, then show relatively poor tearability, and easily contraction distortion in heat pressing process.Therefore adhesive consumption is controlled at 5～70 parts by mass and not only makes paper base material have excellent mechanical performance, good processability can also be arranged.
Paper base material by method for preparing can be paper, nonwoven fabric or other any flaky material that utilizes papermaking process to make.The paper machine that papermaking process utilized can adopt fourdrinier forming, cylinder forming or other any forming machine near these two kinds of paper machines, but preferably utilize oblique net paper machine, this former water separation capability is strong, and the long various synthetic fiber of length are suitable for manufacturing paper with pulp.
When the paper base material of making was used to make high-strength structure comb core, synthetic fiber length was 2～20mm, and these synthetic fiber also must have the characteristic of high-strength and high-modulus, can be inorfils, also can be the organic polymer fibers.Inorfil comprises glass fibre, quartz fibre and ceramic fibre; Organic fiber comprises polyamide fiber, polyparaphenylene Ben Bing Er oxazole fiber, Fanglun 1313, Fanglun 1414 and other aramid fiber fibrids.But consider to adopt relatively cheap glass fibre of price and polyamide fiber from the angle that reduces cost.Adhesive is selected the fiber-like adhesive for use.The also available above-mentioned method preparation of increasing the Tg thermosetting resin of this paper base material.
When the paper base material of making is used to make the high saturating ripple comb core of high power, fiber should adopt quartz fibre, polyparaphenylene Ben Bing Er oxazole fiber, Fanglun 1313, Fanglun 1414 and other aramid fiber fibrids, preferably has quartz fibre, Fanglun 1414 and the polyparaphenylene Ben Bing Er oxazole fiber of excellent dielectric properties.The Fanglun 1414 produces KEVLAR29 and the lower KEVLAR149 of hydroscopicity for du pont company, and polyparaphenylene Ben Bing Er oxazole fiber is that Japanese Japan textile company is produced.Preferred poly fibrid of adhesive and PPTA and polyparaphenylene Ben Bing Er oxazole fine strip body.This paper base material not only light weight, rigidity is big, and hydroscopicity is low, and the dielectric properties excellence is suitable for making the saturating ripple comb core of high power high frequency.
The paper substrate composite that the inventive method prepares has following advantage with respect to prior art:
1. excellent tensile strength, tearability, interlaminar strength, bursting strength and ABRASION RESISTANCE arranged and good pliability is arranged.
2. good heat resistance is arranged, solvent resistance, and good adaptability is arranged with nearly all resin, adhesive and varnish.
3. adopt the high-performance fiber (as quartz fibre, Fanglun 1414 and polyparaphenylene Ben Bing Er oxazole fiber) of excellent dielectric properties and the cellular material that high performance adhesive (poly fibrid and PPTA and polyparaphenylene Ben Bing Er oxazole fine strip body) is made, not only has high-strength and high-modulus, and hydroscopicity is low, the dielectric properties excellence.
4. can adjust the manufacturing technique of paper base material according to economy, purposes and performance several respects.
The specific embodiment
Embodiment 1
In mass fraction, 30 parts of Fanglun 1313s and 70 parts of polyisophthaloyl metaphenylene diamide pulps are broken up with beater respectively, be dispersed in the water mixed 0.05% the water slurry that gets.Obtain body paper by moulding on the Tappi standard handsheet former.Body paper is hot-forming at 320 ℃, 25MPa with flat-bed press then, makes paper base material, and its physical property is as follows: 1. thickness: 0.08mm; 2. quantitative: 75g/m
23. tensile strength: 4.0KN/m; 4. percentage elongation: 7%; 5. tearability: 1.0N; 6. dielectric constant (under the 1GHz): 4.0; 7. dielectric loss factor (under the 1GHz): 0.035.
Embodiment 2
In mass fraction, 0.01% water slurry that is configured to according to the described method of embodiment with 80 parts glass fibres and 20 parts of water-soluble epoxy resins and sulfuric acid.The concentration of sulfuric acid in the aqueous solution is 0.5%.Water slurry obtains body paper by moulding on the Tappi standard handsheet former.Use flat-bed press hot-forming to body paper under 180 ℃, 15MPa, make paper base material, its physical property is as follows: 1. thickness: 0.15mm; 2. quantitative: 75g/m
23. tensile strength: 2.3KN/m; 4. percentage elongation: 3.3%; 7. tearability: 1.0N; 8. dielectric constant (under the 1GHz): 4.9; 9. dielectric loss factor (under the 1GHz): 0.04.
Embodiment 3
In mass fraction, be configured to 0.003% water slurry according to the described method of embodiment with 70 parts polyparaphenylene Ben Bing Er oxazole fibers and 30 parts of water-soluble epoxy resins and cationic polyacrylamide (PAM).The concentration of cationic polyacrylamide (PAM) in the aqueous solution is 0.008%.Water slurry obtains body paper by moulding on the Tappi standard handsheet former.Body paper uses roller mill 150 ℃ of temperature, under the 20Kg/cm linear pressure body paper is carried out hot-formingly, makes paper base material.
Embodiment 4
The paper substrate composite body paper of present embodiment is according to embodiment 1 described forming method preparation.PPTA fine strip body (mass fraction meter) with 70 parts polyparaphenylene Ben Bing Er oxazole fibers and 30 parts is made 0.001% water slurry.Dispersant is an octadecylamine, and its concentration in the aqueous solution is 1%.Body paper uses roller mill 360 ℃ of temperature at last, under the 400Kg/cm linear pressure body paper is carried out hot-formingly, makes paper base material.
Embodiment 5:
In mass fraction, 60 parts of Fanglun 1313s and 40 parts of polyester fibers are broken up with beater respectively.Add the dispersing aid that neopelex 0.001% (concentration in the aqueous solution), cationic polyacrylamide (PAM) 0.008% (concentration in the aqueous solution) and sodium phosphate 0.001% (concentration in the aqueous solution) are formed then, be dispersed in the water mixed 0.03% the water slurry that gets.Use oblique net former wet moulding, dehydrate, obtain body paper.Body paper uses roller mill 220 ℃ of temperature at last, carries out hot-forming to body paper under the 200Kg/cm linear pressure.The physical property of the paper base material that makes is as follows: 1. thickness: 0.10mm; 2. quantitative: 75g/m
23. machine direction tensile strength: 5.4KN/m; 4. cross direction tensile strength: 3.2KN/m; 5. longitudinal tensile strain rate: 11%; 6. cross direction elongation: 7%; 7. tearability: 1.5N.
Embodiment 6
The paper substrate composite body paper of present embodiment is to make with 95 parts Fanglun 1414 and 0.01% water slurry of 5 parts of water-soluble epoxy resins (mass fraction meter) composition according to embodiment 5 described forming methods.Dispersant is neopelex 0.03% (concentration in the aqueous solution), cationic polyacrylamide (PAM) 0.05% (concentration in the aqueous solution) and hydrochloric acid 0.002% (concentration in the aqueous solution).Body paper uses roller mill 180 ℃ of temperature at last, carries out hot-forming under the 200Kg/cm linear pressure.The physical property of the paper base material that makes is as follows: 1. thickness: 0.14mm; 2. quantitative: 75g/m
23. machine direction tensile strength: 3.2KN/m; 4. cross direction tensile strength: 2.1KN/m; 5. longitudinal tensile strain rate: 3.0%; 6. cross direction elongation: 2.2%; 7. tearability: 1N; 8. dielectric constant (under the 1GHz): 3.8; 9. dielectric loss factor (under the 1GHz): 0.025.
Embodiment 7
The paper substrate composite body paper of present embodiment is to make according to 0.01% water slurry that embodiment 5 described forming methods are formed with 85 parts Fanglun 1414 and 15 parts of poly fibrids (mass fraction meter).Dispersant is neopelex 0.005% (concentration in the aqueous solution), sodium alginate 0.005% (concentration in the aqueous solution).Body paper uses flat-bed press hot-forming at 300 ℃, 20MPa at last, carries out hot-forming down.The physical property of the paper base material that makes is as follows: 1. thickness: 0.13mm; 2. quantitative: 75g/m
23. machine direction tensile strength: 3.5KN/m; 4. cross direction tensile strength: 2.3KN/m; 5. longitudinal tensile strain rate: 3.0%; 6. cross direction elongation: 2.2%; 7. tearability: 1.5N; 8. dielectric constant (under the 1GHz): 3.8; 9. dielectric loss factor (under the 1GHz): 0.025.
Embodiment 8
The paper substrate composite body paper of present embodiment is to make according to 0.01% water slurry that embodiment 5 described forming methods are formed with quartz fibre and 20 parts of poly fibrids (mass fraction meter) of 60 parts Fanglun 1414 and 20 parts.Dispersant is Brij-721 0.01% (concentration in the aqueous solution) and cationic polyacrylamide (PAM) 0.01% (concentration in the aqueous solution).Body paper uses roller mill 260 ℃ of temperature at last, carries out hot-formingly under the 300Kg/cm linear pressure, makes paper base material, and its physical property is as follows: 1. thickness: 0.13mm; 2. quantitative: 75g/m
23. machine direction tensile strength: 4.2KN/m; 4. cross direction tensile strength: 3.4KN/m; 5. longitudinal tensile strain rate: 3.3%; 6. cross direction elongation: 3.2%; 7. tearability: 1N; 8. dielectric constant (under the 1GHz): 3.4; 9. dielectric loss factor (under the 1GHz): 0.022.
Embodiment 9
The paper substrate composite body paper of present embodiment is to make according to 0.001% water slurry that embodiment 5 described forming methods are formed with PPTA fine strip body and 20 parts of poly fibrids (mass fraction meter) of 60 parts polyparaphenylene Ben Bing Er oxazole fiber and 20 parts.Dispersant is octadecyl benzene sulfonic acid sodium salt 0.1% (concentration in the aqueous solution) and cationic polyacrylamide (PAM) 0.5% (concentration in the aqueous solution).Body paper uses roller mill 280 ℃ of temperature at last, carries out hot-forming to body paper under the 300Kg/cm linear pressure.The physical property of the paper base material that makes is as follows: 1. thickness: 0.13mm; 2. quantitative: 75g/m
23. machine direction tensile strength: 4.0KN/m; 4. cross direction tensile strength: 3.2KN/m; 5. longitudinal tensile strain rate: 2.5%; (6. cross direction elongation: 1.9%; 7. tearability: 1N; 8. dielectric constant (under the 1GHz): 3.6; 9. dielectric loss factor (under the 1GHz): 0.023.
Claims (8)
1, a kind of preparation method who is used to prepare the paper substrate composite of comb core is characterized in that comprising the steps:
(1) 30～95 parts by mass fibers and 5～70 parts by mass adhesives are broken up with beater, added dispersant, make fiber and binder concn and be 0.001～0.05% water slurry, the concentration of dispersant in water slurry is 0～1% quality;
(2) the papermaking wet moulding dehydrates;
(3) hot-forming;
Described fiber is inorfil and/or synthetic fiber;
Described adhesive is that thermosetting resin, thermoplastic resin fibre or fibrid are or/and fine strip body;
Described dispersant is one or more the mixture in surfactant, water-soluble high-molecular compound, acid and/or the inorganic salts.
2,, it is characterized in that described inorfil is one or more in glass fibre, quartz fibre, the ceramic fibre according to right 1 described preparation method; Described synthetic fiber are one or more among polyamide fiber, polyparaphenylene Ben Bing Er oxazole fiber, Fanglun 1313, the Fanglun 1414.
3,, it is characterized in that described thermosetting resin is epoxy resin, phenolic resins, melamine resin, isocyanate resin or polyimide resin according to right 1 described preparation method; Described thermoplastic resin fibre is polyesters staple fibre or polyamide-based fiber; Described fibrid is polyamide, polyester or poly fibrid; Described fine strip body is PPTA or polyparaphenylene Ben Bing Er oxazole fine strip body.
4,, it is characterized in that described dispersing aid is wherein one or more of surfactant, water-soluble high-molecular compound, acid, inorganic salts according to right 1 described preparation method.
5,, it is characterized in that described surfactant is quaternary amine, soap, Sulfonates or polyethylene glycol oxide according to right 4 described preparation methods; Described water-soluble high-molecular compound is polyacrylic acid or its copolymer analog, polyvinyl alcohol or derivatives thereof class, natural polymer derivatives class; Described acid comprises hydrochloric acid or sulfuric acid.
6,, it is characterized in that step (2) adopts oblique net former to carry out wet moulding according to right 1 described preparation method.
7, according to right 1 described preparation method, it is characterized in that step (3) use roller mill 150～360 ℃ of temperature, 20～400Kg/cm linear pressure is following or use flat-bed press 180～320 ℃ of temperature, carries out hot-forming under 15～25MPa pressure.
8, the paper substrate composite that is used to prepare comb core of the described method preparation of one of claim 1-7.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101595260B (en) * | 2006-12-15 | 2012-06-13 | 纳幕尔杜邦公司 | Honeycomb from controlled porosity paper |
| CN102535223A (en) * | 2010-12-09 | 2012-07-04 | 烟台泰和新材料股份有限公司 | Method for preparing and grading contrapuntal aramid pulp |
| WO2012100648A1 (en) * | 2011-01-27 | 2012-08-02 | 深圳昊天龙邦复合材料有限公司 | Prepreg comprising aromatic synthetic fiber paper and printed circuit board made using the prepreg |
| WO2012100653A1 (en) * | 2011-01-27 | 2012-08-02 | 深圳昊天龙邦复合材料有限公司 | Aramid honeycomb core board |
| CN101557923B (en) * | 2006-12-15 | 2013-03-13 | 纳幕尔杜邦公司 | Processes for making shaped honeycomb and honeycombs made thereby |
| CN103306157A (en) * | 2013-05-29 | 2013-09-18 | 南通大学 | Thermal insulation fireproof composite material and preparation method thereof |
| CN109295793A (en) * | 2018-09-26 | 2019-02-01 | 扬州市祥华新材料科技有限公司 | A kind of preparation method of non-composite type laser paper |
| CN110331619A (en) * | 2019-06-18 | 2019-10-15 | 宁波市嘉化新材料科技有限公司 | A kind of coal ash fiber is used to substitute the enhancing modified technique of part waste paper |
| CN112726283A (en) * | 2020-12-25 | 2021-04-30 | 烟台民士达特种纸业股份有限公司 | Poly (p-phenylene benzobisoxazole) fiber paper base material for high-temperature-resistant honeycomb core material and preparation method thereof |
| CN114892443A (en) * | 2022-05-05 | 2022-08-12 | 华南理工大学 | High-strength high-permeability interlaminar toughened synthetic fiber paper base material and preparation method and application thereof |
| CN115948935A (en) * | 2022-12-22 | 2023-04-11 | 华南理工大学 | High-temperature-resistant carbon fiber paper, honeycomb core material and preparation method thereof |
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- 2005-06-20 CN CN 200510035260 patent/CN1710195A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101557923B (en) * | 2006-12-15 | 2013-03-13 | 纳幕尔杜邦公司 | Processes for making shaped honeycomb and honeycombs made thereby |
| CN101595260B (en) * | 2006-12-15 | 2012-06-13 | 纳幕尔杜邦公司 | Honeycomb from controlled porosity paper |
| CN102535223A (en) * | 2010-12-09 | 2012-07-04 | 烟台泰和新材料股份有限公司 | Method for preparing and grading contrapuntal aramid pulp |
| CN102535223B (en) * | 2010-12-09 | 2014-10-01 | 烟台泰和新材料股份有限公司 | Method for preparing and grading contrapuntal aramid pulp |
| CN103476989A (en) * | 2011-01-27 | 2013-12-25 | 深圳昊天龙邦复合材料有限公司 | Prepreg comprising aromatic synthetic fiber paper and printed circuit board made using the prepreg |
| WO2012100653A1 (en) * | 2011-01-27 | 2012-08-02 | 深圳昊天龙邦复合材料有限公司 | Aramid honeycomb core board |
| CN103502532A (en) * | 2011-01-27 | 2014-01-08 | 深圳昊天龙邦复合材料有限公司 | Aramid honeycomb core board |
| WO2012100648A1 (en) * | 2011-01-27 | 2012-08-02 | 深圳昊天龙邦复合材料有限公司 | Prepreg comprising aromatic synthetic fiber paper and printed circuit board made using the prepreg |
| CN103306157A (en) * | 2013-05-29 | 2013-09-18 | 南通大学 | Thermal insulation fireproof composite material and preparation method thereof |
| CN109295793A (en) * | 2018-09-26 | 2019-02-01 | 扬州市祥华新材料科技有限公司 | A kind of preparation method of non-composite type laser paper |
| CN110331619A (en) * | 2019-06-18 | 2019-10-15 | 宁波市嘉化新材料科技有限公司 | A kind of coal ash fiber is used to substitute the enhancing modified technique of part waste paper |
| CN112726283A (en) * | 2020-12-25 | 2021-04-30 | 烟台民士达特种纸业股份有限公司 | Poly (p-phenylene benzobisoxazole) fiber paper base material for high-temperature-resistant honeycomb core material and preparation method thereof |
| CN114892443A (en) * | 2022-05-05 | 2022-08-12 | 华南理工大学 | High-strength high-permeability interlaminar toughened synthetic fiber paper base material and preparation method and application thereof |
| CN115948935A (en) * | 2022-12-22 | 2023-04-11 | 华南理工大学 | High-temperature-resistant carbon fiber paper, honeycomb core material and preparation method thereof |
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