CN103703046A - Paper structures impregnated with polyurea, and process for production thereof - Google Patents

Paper structures impregnated with polyurea, and process for production thereof Download PDF

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Publication number
CN103703046A
CN103703046A CN201280037726.1A CN201280037726A CN103703046A CN 103703046 A CN103703046 A CN 103703046A CN 201280037726 A CN201280037726 A CN 201280037726A CN 103703046 A CN103703046 A CN 103703046A
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CN
China
Prior art keywords
weight
diphenylmethanediisocyanate
nco
prepolymer
water
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Pending
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CN201280037726.1A
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Chinese (zh)
Inventor
R.阿尔巴赫
H-D.阿恩茨
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Bayer Pharma AG
Bayer Intellectual Property GmbH
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Bayer Pharma AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to pressure-resistant and flexurally stiff paper structures impregnated with urethane-modified polyurea, and to a process for production thereof.

Description

Paper structure and manufacture method thereof with polyureas dipping
The present invention relates to paper structure of the urethane-modified polyureas dipping of the use of resistance to compression and bending resistance and preparation method thereof.
In the structure of load larrying member, for example, in automobile construction, use sandwich component for weight reduction.Described sandwich component consists of the sandwich layer of lightweight and the solid surface layer that sticks to both sides.As the sandwich layer of lightweight, use to obtain the rigid foam of self-polystyrene, urethane, plastic fabric or paper structure, for example paper honeycomb.As surface layer, especially can use glued board, glass filament reinforced plastics or tinsel.
The object of this matrix material is, in the situation that as far as possible little weight realizes maximum load-carrying capacity.But when using cheap paper honeycomb, wet sensitive is a barrier.In order to improve the portative power of paper honeycomb under wet condition, conventionally it is also made to its reinforcement thus with synthetic resins dipping.Corresponding suitable synthetic resins can be formaldehyde condensation products (US-A 6372322) and vibrin.Synthetic resins based on isocyanic ester has also been described.The combination of Synolac and isocyanic ester is also known (US-A 2744042).
W. the people such as J. McKillip describes tolylene diisocyanate and is better than aliphatic isocyanate.According to this author, methylenediphenyl diisocyanates is better than again tolylene diisocyanate at it aspect reactive.
In US-A 5008359, show, the diphenylmethanediisocyanate of polymerization (MDI) is suitable.Here clearly without catalyzer.
US-A 5292391 and the cheap unmodified polymerization diphenylmethanediisocyanate (MDI) of the same use of US-A 5332458.The polymeric MDI using in US-A 5580243 has the monomer 4 of 40-60%, and 4'-diphenylmethanediisocyanate content also has wide functionality and range of viscosities.
In US-A 5140086, disclose with organic solvent, especially used propylene glycol, the raising that dilution polymerization diphenylmethanediisocyanate brings speed of response.Vanay and triethyl citrate (US-A 5580922) and phosphoric acid ester (US-A 5580243) are described to solvent and fire retardant equally, and correspondingly use.
Being described in sandwich component in DE-A 102006016943, DE-A 102008033559 and DE-A 102008051436 makes by having the core material with isocyanic ester-improved paper honeycomb of having improved ultimate compression strength.
Therefore, the object of this invention is to provide paper structure, its a) do not comprise solvent or do not use solvent make and therefore can be used for indoor, b) can have no problem ground and make at short notice supporting member and c) use enough hydrophilic synthetic resins to be used for its moisture curing.Bending rigidity or resistance to compression rigidity that the paper structure so obtaining answers tool to be significantly improved.
Surprisingly, described object can be by being achieved with the paper structure of polyureas-dipping, wherein with the isocyanic ester using in dipping containing the long-chain polyether chemical modification of ethylene oxide.Can improve the hardness of described paper structure thus, although owing to obviously reducing with the polyether-modified content of the isocyanate groups of requisite every mass unit for described paper structure and polyureas crosslinked that makes in used isocyanic ester.In addition surprisingly, the introducing of soft segment in polyureas (modification of the isocyanic ester that the polyethers that must use by oneself containing ethylene oxide carries out) causes the improvement of hardness and bending rigidity.
Theme of the present invention is by by isocyanic ester dipping and the method for reacting subsequently the paper structure of preparation resistance to compression and bending resistance with water, water vapor and/or air moisture, it is characterized in that,
I) by least one or the multiple NCO-prepolymer with carbamate groups, flood described paper structure, wherein, described NCO-prepolymer has the NCO-content of 18-27 % by weight, and wherein said prepolymer is the reaction product of following substances:
A) diphenylmethanediisocyanate-isomer and optional they higher homologue and optionally there are at least 50 % by weight, the diphenylmethanediisocyanate of the modification of preferred 60-90 % by weight monomer diphenylmethanediisocyanate, with
B) polyalkylene oxide of polymerization, its per molecule has 1.8-8, preferred 2-6,3-6 isocyanate-reactive group (number-average) there is at least 5-100 % by weight based on polyalkylene oxide meter particularly preferably, preferred 13-90 % by weight at least, 17-90 % by weight at least particularly preferably, the very particularly preferably ethylene oxide unit of 25-85 % by weight at least, and/or there is the polycarbonate polyol that molecular weight is the polymerization of 1000-15000
Optionally mix with the diphenylmethanediisocyanate of modification
With
Ii) described at least one or multiple NCO-prepolymer are reacted with water, water vapor and/or air moisture.
Described polyalkylene oxide preferably has 1000-15000, and the particularly preferably molecular weight of 3000-13000, and the polycarbonate polyol that can be partially or completely 1000-15000 by molecular weight substitutes.
Preferably, catalyzer is added in described prepolymer with the amount of 0.05-1 % by weight, based on component A) and summation meter B).Use metallic catalyzer as preferred catalyzer.
In a preferred process program, will add in water as normally used catalyzer in polyurethane chemistry.Described catalyzer comprises for example carboxylate, phenates, amine oxide, and tertiary amine catalyst particularly preferably, and in the amount for curing water 0.05-40 % by weight based on being used, its per molecule preferably comprises 2-4 hydroxyl.As preferred amine catalyst, for example can mention: each quadrol has the oxyalkylated quadrol of 3-8 molecular oxidation propylene, oxyalkylated trolamine and other oxyalkylated amine, optionally mix with triethylenediamine and/or the known tertiary amine of five methyl diethylentriamine, dimethyl benzylamine or other prior art.
The weight ratio of 4,4'-diphenylmethanediisocyanate and 2,4'-diphenylmethanediisocyanate is preferably 5:1-1:2.
The diphenylmethanediisocyanate of modification, for example uretonimine (uretonimines), carbodiimide or isocyanuric acid ester, also can be used as preparing the isocyanate component of NCO-prepolymer.
For improving the resistivity against fire of this reinforcement paper structure, particularly advantageously to for example adding in described NCO-prepolymer, by the known liquid or solid fire retardant of prior art (organic and/or inorganic phosphate or phosphite, expansible black lead).
Another theme of the present invention is to have the resistance to compression of polyureas dipping of carbamate groups and the paper structure of bending resistance with at least one, and the wherein said polyureas with carbamate groups can derive from
A) one or more have the NCO-prepolymer of carbamate groups, and the NCO-content that it has 18-27 % by weight, can derive from
A) diphenylmethanediisocyanate-isomer and optional they higher homologue and optionally there are at least 50 % by weight, the diphenylmethanediisocyanate of the modification of preferred 60-90 % by weight monomer diphenylmethanediisocyanate, with
B) polyalkylene oxide of polymerization, its per molecule has 1.8-8, preferred 2-6,3-6 isocyanate-reactive group (number-average) there is at least 5-100 % by weight based on polyalkylene oxide meter particularly preferably, preferred 13-90 % by weight at least, 17-90 % by weight at least particularly preferably, the very particularly preferably ethylene oxide unit of 25-85 % by weight at least, and/or there is the polycarbonate polyol that molecular weight is the polymerization of 1000-15000
A') optionally mix with the diphenylmethanediisocyanate of modification, and
B) water, water vapor and/or air moisture.
Another theme of the present invention is sandwich component, it is characterized in that, it has
I) core of being made by paper structure according to the present invention and
Ii) at least one deck be positioned at described core two sides at least one side on fibre-reinforced polyureas and/or the layer of urethane.
The dipping of described paper structure is for example undertaken by this paper structure being immersed in prepolymer or by prepolymer being applied on paper structure or by spray this paper structure with prepolymer.
The weight level of paper, the quality of paper (according to fibrous texture definition) and honeycomb size have interaction to (the resistance to compression)-intensity of honeycomb.
After on coated material (NCO-prepolymer) being applied to paper structure (preferably paper honeycomb), it should preferably permeate until enter in the fiber of this paper structure.Therefore, preferably use the receptivity that had on the one hand and on the other hand when dipping not too swelling also lose thus the quality of the paper of structure and intensity.
For optimizing the use (NCO-prepolymer) of material, after impregnated paper structure, preferably from paper structure, remove excessive coated material (NCO-prepolymer), for example, by knocking out, wipe or by dry pressurized air or other dry pressurized gas.
By adding subsequently water, for example by spraying, by flooding or water, this NCO-prepolymer reacts, and dissociates carbonic acid gas and forms foam, this foam also can be clogged the inside of this paper structure (for example paper honeycomb).
By according to the dipping of paper structure of the present invention, can make its waterproof, chemicals-resistant and than the bending resistance significantly more of undressed paper structure.Therefore, they are also applicable to outdoor field.
Described reinforcement paper structure can be used as manufacturing the interval insulant of sandwich component.
Can further illustrate the present invention by the following examples.
embodiment:
Initial compounds:
Isocyanic ester A is the NCO-prepolymer based on diphenylmethanediisocyanate, and it has NCO-content is that 23 % by weight and the viscosity at 25 ℃ are 405 mPas.The polyalkylene oxide that it comprises the polymerization of 25 % by weight based on glycerol, described polyalkylene oxide has 4500 weight-average molecular weight and the ethylene oxide content of 73 % by weight.The MDI using has the monomer M DI of 83 % by weight and the uretonimine of 6 % by weight, and described monomer M DI has 4 of 2.9:1, the weight ratio of 4'-MDI and 2,4'-MDI.
Isocyanic ester B is the NCO-prepolymer based on diphenylmethanediisocyanate, and it has NCO-content is that 21.3 % by weight and the viscosity at 25 ℃ are 680 mPas.The polyalkylene oxide that it comprises the polymerization of 31 % by weight based on propylene glycol and glycerol, described polyalkylene oxide has 3830 weight-average molecular weight and the ethylene oxide content of 61 % by weight.The MDI using has the monomer M DI of 72 % by weight, and described monomer M DI has 4 of 2.2:1, the weight ratio of 4'-MDI and 2,4'-MDI.
Isocyanic ester C is the NCO-prepolymer based on diphenylmethanediisocyanate, and it has NCO-content is that 22 % by weight and the viscosity at 25 ℃ are 750 mPas.The polyalkylene oxide that it comprises the polymerization of 24.7 % by weight based on propylene glycol and glycerol, described polyalkylene oxide has 4840 weight-average molecular weight and the ethylene oxide content of 17 % by weight.The MDI using has the monomer M DI of 60 % by weight, and described monomer M DI has 4 of 2.9:1, the weight ratio of 4'-MDI and 2,4'-MDI.
Isocyanic ester D is the NCO-prepolymer based on diphenylmethanediisocyanate, and it has NCO-content is that 23.5 % by weight and the viscosity at 25 ℃ are 534 mPas.The polyalkylene oxide that it comprises the polymerization of 24.7 % by weight based on glycerol, described polyalkylene oxide has 6000 weight-average molecular weight and the ethylene oxide content of 17 % by weight.The MDI using has the monomer M DI of 53 % by weight and the uretonimine of about 2 % by weight, and described monomer M DI has 4 of 2.4:1, the weight ratio of 4'-MDI and 2,4'-MDI.
Isocyanic ester E is that its viscosity that has at 25 ℃ is the NCO-content of 63 mPas and about 24 % by weight with the diphenylmethanediisocyanate of the unmodified polymerization of propylene carbonate dilution.
The paper honeycomb using has the honeycomb diameter of 5 mm, and the height of 6.5 mm and 430 g/m2's is quantitative.
The execution of experiment:
At room temperature described paper is immersed in corresponding isocyanic ester, and by paper pulp, is removing after excessive isocyanic ester, with the water that does not add catalyzer at 80 ℃ of time chien shih cured with isocyanates through 24 hours.
On the paper honeycomb through so flooding, according to DIN EN ISO 826, record ultimate compression strength and record bending strength according to DIN EN ISO 178.Result provides in following table:
Table:
Figure 363659DEST_PATH_IMAGE001
* according to DIN ISO 845
Bending strength is measured with the span of constant 80mm.
From this table, compared to using polymeric MDI (isocyanic ester E), use NCO-prepolymer A, B, C and D to give bending strength and/or the ultimate compression strength that paper structure improves.

Claims (6)

1. the method for the paper structure of preparation resistance to compression and bending resistance, described method, by with isocyanic ester dipping with react and carry out with water, water vapor and/or air moisture subsequently, is characterized in that,
I) by least one or the multiple NCO-prepolymer with carbamate groups, flood described paper structure, wherein, described NCO-prepolymer has the NCO-content of 18-27 % by weight, and wherein said prepolymer is the reaction product of following substances:
A) diphenylmethanediisocyanate-isomer and optional they higher homologue and optionally there is the diphenylmethanediisocyanate of modification of the monomer diphenylmethanediisocyanate of at least 50 % by weight, with
B) polyalkylene oxide of polymerization, its per molecule has 1.8-8 isocyanate-reactive group and has the ethylene oxide unit of at least 5-100 % by weight based on polyalkylene oxide meter, and/or has the polycarbonate polyol that molecular weight is the polymerization of 1000-15000,
Optionally mix with the diphenylmethanediisocyanate of modification
With
Ii) described at least one or multiple NCO-prepolymer are reacted with water, water vapor and/or air moisture.
2. according to the method for claim 1, it is characterized in that, catalyzer is added in described NCO-prepolymer with the amount of 0.05-1 % by weight, based on described NCO-prepolymer meter.
3. according to the method for claim 1, it is characterized in that, the tertiary amine catalyst by per molecule containing 2-4 hydroxyl adds in water with the amount of 0.05-40 % by weight, the water meter based on used.
4. according to the method for claim 1, it is characterized in that, the weight ratio of 4,4'-diphenylmethanediisocyanate and 2,4'-diphenylmethanediisocyanate is 5:1-1:2.
5. the resistance to compression and the bending resistance paper structure that with at least one, have the polyureas dipping of carbamate groups, the wherein said polyureas with carbamate groups can derive from
A) one or more have the NCO-prepolymer of carbamate groups, and the NCO-content that it has 18-27 % by weight, can derive from
A) diphenylmethanediisocyanate-isomer and optional they higher homologue and optionally there is the diphenylmethanediisocyanate of modification of the monomer diphenylmethanediisocyanate of at least 50 % by weight, with
B) polyalkylene oxide of polymerization, its per molecule has 1.8-8 isocyanate-reactive group and has the ethylene oxide unit of at least 5-100 % by weight based on polyalkylene oxide meter, and/or has the polycarbonate polyol that molecular weight is the polymerization of 1000-15000,
A') optionally mix with the diphenylmethanediisocyanate of modification, and
B) water, water vapor and/or air moisture.
6. sandwich component, is characterized in that, described sandwich structure has
I) by the core of making according to the paper structure of claim 5 and
Ii) at least one deck be positioned at described core two sides at least one side on fibre-reinforced polyureas and/or the layer of urethane.
CN201280037726.1A 2011-07-29 2012-07-25 Paper structures impregnated with polyurea, and process for production thereof Pending CN103703046A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102011080090 2011-07-29
DE102011080090.5 2011-07-29
PCT/EP2012/064624 WO2013017508A1 (en) 2011-07-29 2012-07-25 Paper structures impregnated with polyurea, and a process for production thereof

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Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744042A (en) 1951-06-21 1956-05-01 Goodyear Tire & Rubber Laminated panels
SE357222B (en) * 1968-08-27 1973-06-18 Takeda Chemical Industries Ltd
US5140086A (en) 1988-11-25 1992-08-18 Weyerhaeuser Company Isocyanate modified cellulose products and method for their manufacture
US5008359A (en) 1988-11-25 1991-04-16 Weyerhaeuser Company Isocyanate modified cellulose products and method for their manufacture
US5332458A (en) 1991-04-29 1994-07-26 Weyerhaeuser Co Corrugated paperboard strength enhancing process
US5280097A (en) * 1990-11-27 1994-01-18 Weyerhaeuser Company Laminated composites of polyurea-cellulose and methods for their manufacture
US5292391A (en) 1991-04-29 1994-03-08 Wyerhaeuser Company Corrugated paperboard strength enhancing process
WO1993005232A1 (en) * 1991-08-30 1993-03-18 Weyerhaeuser Company Polyurea-cellulose composites and methods for their manufacture
WO1993007337A1 (en) * 1991-10-02 1993-04-15 Weyerhaeuser Company Polyurea-reinforced fiber-based materials
US5580243A (en) 1995-06-01 1996-12-03 Bloore; John A. Removable orthodontic aligner with eyelet arm springs
US5580922A (en) 1995-06-06 1996-12-03 Weyerhaeuser Company Cellulose products treated with isocyanate compositions
US6372322B1 (en) 1998-05-28 2002-04-16 Pactiv Corporation Shaped honeycomb structures and method and apparatus for making shaped honeycomb structures
DE102006016943A1 (en) 2006-04-11 2007-10-25 Gundelsheimer, Hildegard Optimization of paper quality for application in loaded element by coating/impregnating a chemical e.g. polyurethane/polyester synthetic material, where the fiber structure of the paper is strengthened and solidified
DE102008033559A1 (en) 2008-09-09 2010-03-11 Herbert Gundelsheimer Component e.g. door panel, has upper and lower covering layers made of glass-fiber reinforced plastic or plastic reinforced fibers e.g. carbon fibers, and middle layer consisting of honeycomb construction
DE102008051436A1 (en) 2008-10-15 2010-04-22 Herbert Gundelsheimer Planar component i.e. supporting component, for mobile home- and caravan industries, has core made of paper honeycomb and enclosed by cover layers, where paper honeycomb and connection of paper honeycomb are coated with cover layers

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WO2013017508A1 (en) 2013-02-07

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