EP0736120A1 - Layered smooth surface aramid papers of high strength and printability - Google Patents

Layered smooth surface aramid papers of high strength and printability

Info

Publication number
EP0736120A1
EP0736120A1 EP95907233A EP95907233A EP0736120A1 EP 0736120 A1 EP0736120 A1 EP 0736120A1 EP 95907233 A EP95907233 A EP 95907233A EP 95907233 A EP95907233 A EP 95907233A EP 0736120 A1 EP0736120 A1 EP 0736120A1
Authority
EP
European Patent Office
Prior art keywords
paper
layer
aramid
weight
floe
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95907233A
Other languages
German (de)
French (fr)
Other versions
EP0736120B1 (en
Inventor
Philip Parks Burks, Jr.
Lee James Hesler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0736120A1 publication Critical patent/EP0736120A1/en
Application granted granted Critical
Publication of EP0736120B1 publication Critical patent/EP0736120B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26Polyamides; Polyimides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30Multi-ply

Definitions

  • This invention relates to an improved layered aramid paper having a smooth surface and good tensile and tear strengths.
  • the smooth surface provides for better print clarity and makes such papers particularly useful for high temperature label applications.
  • Prior art techniques that improve on surface smoothness often lead to a reduced level of mechanical strength and/or thermal stability.
  • synthetic papers which have been pressed or calendered at high temperature and pressure will generally have fibers on the surface which cause roughness or snagging when the surface of the paper is worked during end use processing.
  • This invention provides a multi-layered, smooth surface aramid paper containing from 40 to 55% by weight of fibrids and comprising a substrate layer which consists essentially of aramid fibrids and floe and one or two surface layers each intimately bonded to the substrate layer, said surface layer(s) consisting essentially of from 65 to 90% by weight aramid fibrids and from 10 to 35% by weight aramid floe and comprising from 10 to 67% of the weight of the paper.
  • the paper has a density of 0.8 to 1.0 g/cc with thickness of 1 to 30 mils (0.025 to 0.762 mm) .
  • the multi-layered aramid papers of the invention are comprised of layers of different compositions to provide desired properties.
  • the surface layer(s) provide a smooth surface and contain from 65 to 90% aramid fibrid and from 10% to 35% of aramid floe.
  • the surface layer(s) constitutes from 10 to 67% of the weight of the paper.
  • the substrate layer provides high tear strength. In order for the multi-layered paper to behave as a unitary structure, it is preferred that the fibrous materials at the interface between layers be intermingled.
  • a layer of furnish i.e., a paper- making aqueous dispersion of floe and fibrid on an undried, previously formed layer of furnish in a paper making machine or by simultaneously depositing the layers of different composition on the screen of the paper making machine using a 2 or 3 layer hydraulic type headbox.
  • the paper coming off the machine is dried and calendered, preferably to a thickness of from 1 to 30 mils.
  • the density of the layered paper is preferably from 0.8 to 1.0 g/cc for use as labels.
  • Aramid floe is high temperature resistant floe or short fiber cut from longer aramid fiber, such as those prepared by processes described in U.S. Pat. Nos. 3,063,966; 3,133,138; 3,767,756 and 3,869,430. It refers to short fibers typically having a length of 2 to 12 mm and a linear density of 1-10 deeitex, made of aromatic polyamide which is non-fusible.
  • the aramid fibrids can be prepared using a fibridating apparatus where a polymer solution is precipitated and sheared in a single step as described in U.S. Pat. No. 3,756,908.
  • the tensile break strength of paper is determined based on ASTM method D 828-87 for "Standard Test Method for Tensile Breaking Strength of Paper and Paperboard". Specimens are 2.54 cm wide and 20.3. cm long and the jaws of the tensile testing machine are initially separated by 12.7 cm. Ten paper samples are tested in the machine direction (MD) and ten are tested in the cross direction (CD) and the values for each direction are averaged. The total of the MD and CD strengths is divided by paper density and paper basis weight to obtain the Total Break Strength.
  • MD machine direction
  • CD cross direction
  • Thickness of papers is determined using calipers in accordance with ASTM D 374-79 (1986) .
  • Density of papers is determined by determining the weight per unit area of the paper (Basis Weight) in accordance with ASTM D 646-86 and dividing by the thickness.
  • the number of fibers extending greater than about 0.5 mm above the solid paper surface was taken as the Abraded Fiber Count (per centimeter) and indicates the degree of roughness of the sample.
  • the following examples are illustrative of the invention and are not to be construed as limiting.
  • Example 1 A two layered structure was made by combining fibrids of poly(m-phenylene isophthalamide) prepared as described in Example 1 of U.S. Pat. No. 3,756,908 and floe prepared by dry spinning poly(m-phenylene isophthalamide) from a solution containing 67% dimethyl acetamide (DMAc) , 9% calcium chloride and 4% water.
  • the spun filaments were flooded with an aqueous liquid and contained about 100% DMAc, 45% calcium chloride and 30-100% water based on dry polymer.
  • the filaments were washed and drawn 4X in an extraction-draw process in which the chloride and DMAc contents were reduced to about 0.10% and 0.5%, respectively.
  • the filaments had a denier of 2 (2.2 dtex) and typical properties were: elongation to break, 34%, and tenacity, 4.3 grams/denier (3.8 dN/tex) .
  • the filaments were then cut to floe length of 0.27 inch (0.68 cm) and slurried in water to a concentration of about 0.35%.
  • Blends of fibrids and floe were separately fed to a 2-layer hydraulic type headbox which maintains each blend as a distinct layer until the slice exit where limited mixing of the layers occurs. This allows good bonding between the layers while still maintaining the individual nature of each layer.
  • the formed sheet is then processed as is normally done on a fourdrinier paper machine by pressing and drying.
  • the papers are dried completely using infrared heaters before being calendered at 320"C at a line speed of 30 feet per minute (9 meters per minute) using a pressure of 725 pounds per linear inch (130 kg/cm) .
  • the composition of the layers varied from 35 to
  • Layered structures, 4.0-4.5 oz/yd 2 (135.6- 152.6 g/m 2 ) were produced with high fibrid layers on both top and bottom of the structure.
  • the top and bottom plies (outer layers) had equal basis weight.
  • the top and bottom layers contain 65% fibrid and 35% floe.
  • the top layer was applied using a secondary headbox jetting the furnish onto an already formed sheet which was prepared using the headbox of Example 1.
  • the control (C2-1) was a single layer paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

A multi-layered smooth surface aramid paper with high break strength and tear resistance comprises a substrate layer and at least one surface layer intimately bonded to the substrate layer, wherein the surface layer(s) consists essentially of 65 to 90 % by weight aramid fibrids and 10 to 35 % by weight aramid floc and comprises 10 to 67 % of the total basis weight of the paper.

Description

TITLE
LAYERED SMOOTH SURFACE ARAMID PAPERS OF HIGH STRENGTH AND PRINTABILITY Background of the Invention This invention relates to an improved layered aramid paper having a smooth surface and good tensile and tear strengths. The smooth surface provides for better print clarity and makes such papers particularly useful for high temperature label applications. Prior art techniques that improve on surface smoothness often lead to a reduced level of mechanical strength and/or thermal stability. Moreover, synthetic papers which have been pressed or calendered at high temperature and pressure will generally have fibers on the surface which cause roughness or snagging when the surface of the paper is worked during end use processing.
Summary of the Invention
This invention provides a multi-layered, smooth surface aramid paper containing from 40 to 55% by weight of fibrids and comprising a substrate layer which consists essentially of aramid fibrids and floe and one or two surface layers each intimately bonded to the substrate layer, said surface layer(s) consisting essentially of from 65 to 90% by weight aramid fibrids and from 10 to 35% by weight aramid floe and comprising from 10 to 67% of the weight of the paper. Preferably, the paper has a density of 0.8 to 1.0 g/cc with thickness of 1 to 30 mils (0.025 to 0.762 mm) .
Detailed Description of the Invention
The multi-layered aramid papers of the invention are comprised of layers of different compositions to provide desired properties. The surface layer(s) provide a smooth surface and contain from 65 to 90% aramid fibrid and from 10% to 35% of aramid floe. The surface layer(s) constitutes from 10 to 67% of the weight of the paper. The substrate layer provides high tear strength. In order for the multi-layered paper to behave as a unitary structure, it is preferred that the fibrous materials at the interface between layers be intermingled. This is achieved by depositing a layer of furnish, i.e., a paper- making aqueous dispersion of floe and fibrid on an undried, previously formed layer of furnish in a paper making machine or by simultaneously depositing the layers of different composition on the screen of the paper making machine using a 2 or 3 layer hydraulic type headbox. The paper coming off the machine is dried and calendered, preferably to a thickness of from 1 to 30 mils. The density of the layered paper is preferably from 0.8 to 1.0 g/cc for use as labels.
It has been found that the multi-layered papers of this invention have excellent mechanical properties. The smooth surface retains a high degree of smoothness even after the necessary working to prepare it for end use applications. This quality is important if print clarity and color density is to be achieved. Aramid floe is high temperature resistant floe or short fiber cut from longer aramid fiber, such as those prepared by processes described in U.S. Pat. Nos. 3,063,966; 3,133,138; 3,767,756 and 3,869,430. It refers to short fibers typically having a length of 2 to 12 mm and a linear density of 1-10 deeitex, made of aromatic polyamide which is non-fusible.
The aramid fibrids can be prepared using a fibridating apparatus where a polymer solution is precipitated and sheared in a single step as described in U.S. Pat. No. 3,756,908.
Tests and Measurements
Total Break Strength. The tensile break strength of paper is determined based on ASTM method D 828-87 for "Standard Test Method for Tensile Breaking Strength of Paper and Paperboard". Specimens are 2.54 cm wide and 20.3. cm long and the jaws of the tensile testing machine are initially separated by 12.7 cm. Ten paper samples are tested in the machine direction (MD) and ten are tested in the cross direction (CD) and the values for each direction are averaged. The total of the MD and CD strengths is divided by paper density and paper basis weight to obtain the Total Break Strength.
Thickness. Thickness of papers is determined using calipers in accordance with ASTM D 374-79 (1986) .
Density. Density of papers is determined by determining the weight per unit area of the paper (Basis Weight) in accordance with ASTM D 646-86 and dividing by the thickness.
Abraded Fiber Count.
In order to further investigate the abrasion qualities of these papers, the papers were folded and the edge of the fold was viewed against a dark background.
The number of fibers extending greater than about 0.5 mm above the solid paper surface was taken as the Abraded Fiber Count (per centimeter) and indicates the degree of roughness of the sample. The following examples are illustrative of the invention and are not to be construed as limiting.
EXAMPLES Example 1 A two layered structure was made by combining fibrids of poly(m-phenylene isophthalamide) prepared as described in Example 1 of U.S. Pat. No. 3,756,908 and floe prepared by dry spinning poly(m-phenylene isophthalamide) from a solution containing 67% dimethyl acetamide (DMAc) , 9% calcium chloride and 4% water. The spun filaments were flooded with an aqueous liquid and contained about 100% DMAc, 45% calcium chloride and 30-100% water based on dry polymer. The filaments were washed and drawn 4X in an extraction-draw process in which the chloride and DMAc contents were reduced to about 0.10% and 0.5%, respectively. The filaments had a denier of 2 (2.2 dtex) and typical properties were: elongation to break, 34%, and tenacity, 4.3 grams/denier (3.8 dN/tex) . The filaments were then cut to floe length of 0.27 inch (0.68 cm) and slurried in water to a concentration of about 0.35%.
Blends of fibrids and floe were separately fed to a 2-layer hydraulic type headbox which maintains each blend as a distinct layer until the slice exit where limited mixing of the layers occurs. This allows good bonding between the layers while still maintaining the individual nature of each layer. The formed sheet is then processed as is normally done on a fourdrinier paper machine by pressing and drying.
The papers are dried completely using infrared heaters before being calendered at 320"C at a line speed of 30 feet per minute (9 meters per minute) using a pressure of 725 pounds per linear inch (130 kg/cm) . The composition of the layers varied from 35 to
65% fibrid, the remainder being floe. The basis weight of each layer was adjusted so that the high fibrid layer (65% fibrid) ranged from 33 to 67% of the total basis weight of the final sheet. The total fibrid content of the test papers ranged from 45 to 55% of the sheet versus 53% for the single layer control papers (Cl-1) . Table 1 gives the basis weight of each layer and its composition.
Table 1
Total Sheet Substrate Layer Surface Layer
Run BW aim % % BW aim % % BW aim % % Number g/mi. Fibrid Floe g/mf- Fibrid Floe g/mfi Fibrid Floe
1-1 42 45 55 28 35 65 14 65 35
1-2 42 50 50 21 35 65 21 65 35
1-3 42 55 45 14 35 65 28 65 35
Cl-1 42 53 47 42 53 47 _ — _
The amount of loose fibers on the surfaces of the sheet as a result of mechanical working of the calendered paper was measured (Table 2) . Side 1 is the substrate layer (low fibrid content layer) and Side 2 the surface (high fibrid content) layer. Table 2 Abraded Fiber Count
Fiber Count
Sample (per 5 cm) Number Side 1 Side 2
1-1 20 0
1-2 12 2
1-3 14 0
Cl-1 14 _
Even with the significant reduction in the number of loose fibers on the surface of the high fibrid content papers, superior mechanical properties are maintained versus a control paper of similar average composition but with no layering (Table 3) .
Table 3 Calendered Paper Properties
Sample Number 1-1 1-2 1-3 Cl-1
B.W.*, oz/yd2 1.3 1.5 1.4 1.3
(g/m2) (44.1) (50.9) . (47.5) (44.1)
Thickness, mils 2.0 2.5 2.2 2.4
(mm) (0.051) (0.064) (0.056) (0.061)
Density, g/cc 0.82 0.89 0.86 0.72
B.S.**, lb/in MD/CD 15/7 21/10 18/7 20/8
(N/cm) (26/12) (37/18) (32/12) (35/14)
Eb***, MD/CD 4/3 6/3 5/2 6/3
Elmendorf Tear, 108/191 120/193 87/166 127/215 g MD/CD
(N) (1.06/1.87) (1.18/1.89) (0.85/1.63)1 (1.25/2.1
Shrinkage @ 300°C, 2/0 2/0 2/0 2/0 % MD/CD
* Basis Weight
** Break Strength
*** Break Elongation Example 2
Layered structures, 4.0-4.5 oz/yd2 (135.6- 152.6 g/m2) were produced with high fibrid layers on both top and bottom of the structure. The top and bottom plies (outer layers) had equal basis weight. The top and bottom layers contain 65% fibrid and 35% floe. The top layer was applied using a secondary headbox jetting the furnish onto an already formed sheet which was prepared using the headbox of Example 1. The control (C2-1) was a single layer paper.
Table 4
Total Sheet Each Outer Layer Inner (Substrate) Layer
Run BW aim % % BW aim % % BW aim % % Number g/mi Fibrid Floe gm Fibrid Floe g/m Fibrid Floe
2-1 132 46 54 24 65 35 84 35 65
2-2 132 55 45 44 65 35 44 35 65
C2-1 137 47 137 53 47 _ — — _
Improvement in the amount of loose fibers on the surface as a result of mechanical working of the paper is obvious from Table 5.
Table 5 Abraded Fiber Count
Sample Fiber Count
Number (per 5 cm.
2-1 5 2-2 7
C2-1 12
Even with the major reduction in the number of loose fibers on the surface of the papers superior mechanical properties are maintained versus a control paper of similar average composition but with no layering (Table 6). The low shrinkage at 300°C along with the high tear and tensile properties as compared with the control is especially noteworthy.
Table 6 Calendered Paper Properties
Sample Number 2-1 2-2 C2-1
Basis Weight, oz/yd2 4.3 4.3 4.1 (g/m2) (145.7) (145.8) (139.0)
Thickness, mils 7.5 6.7 6.8
(mm) (0.191) (0.170) (0.173)
Density, g/cc 0.77 0.87 0.80
B.S. , lb/in MD/CD 55/30 61/39 54/33 (N/cm) (96/53) (107/68) (95/58)
Eb, % MD/CD 6/4 9/6 7/5
Elmendorf Tear, g MD/CD D 695/762 421/598 504/662
(N) (6.82/7.48) (4.13/5.87) (4.94/6.49)
Shrinkage §300°C, 1/1 1/1 1/1 % MD/CD

Claims

Claims :
1. A multi-layered smooth surface aramid paper containing from 40 to 55% by weight of fibrids and comprising a substrate layer which consists essentially of aramid fibrids and floe and one or two surface layers, each intimately bonded to the substrate layer, said surface layer(s) comprising from 10 to 67% of the weight of the paper and consisting essentially of from 65 to 90% by weight aramid fibrids and from 10 to 35% by weight aramid floe;
2. The paper of Claim 1 having a density of 0.8 to 1.0 g/cc and a thickness of 1 to 30 mils (0.0254 to 0.762 mm) .
3. The paper of Claim 1, wherein said paper comprises two surface layers intimately bonded to opposite sides of said substrate layer.
EP95907233A 1993-12-21 1994-12-20 Layered smooth surface aramid papers of high strength and printability Expired - Lifetime EP0736120B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17084193A 1993-12-21 1993-12-21
US170841 1993-12-21
PCT/US1994/014672 WO1995017549A1 (en) 1993-12-21 1994-12-20 Layered smooth surface aramid papers of high strength and printability

Publications (2)

Publication Number Publication Date
EP0736120A1 true EP0736120A1 (en) 1996-10-09
EP0736120B1 EP0736120B1 (en) 1998-01-21

Family

ID=22621482

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95907233A Expired - Lifetime EP0736120B1 (en) 1993-12-21 1994-12-20 Layered smooth surface aramid papers of high strength and printability

Country Status (7)

Country Link
EP (1) EP0736120B1 (en)
JP (1) JP3673277B2 (en)
DE (1) DE69408170T2 (en)
ES (1) ES2111394T3 (en)
RU (1) RU2125131C1 (en)
UA (1) UA37254C2 (en)
WO (1) WO1995017549A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230072A1 (en) * 2004-04-16 2005-10-20 Levit Mikhail R Aramid paper blend
US8268434B2 (en) * 2007-11-30 2012-09-18 E I Du Pont De Nemours And Company Honeycomb having a high compression strength and articles made from same
US8114251B2 (en) * 2007-12-21 2012-02-14 E.I. Du Pont De Nemours And Company Papers containing fibrids derived from diamino diphenyl sulfone
US8118975B2 (en) * 2007-12-21 2012-02-21 E. I. Du Pont De Nemours And Company Papers containing fibrids derived from diamino diphenyl sulfone
JP6174120B2 (en) * 2012-04-18 2017-08-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Multilayer sheet
JP6096281B2 (en) * 2012-04-18 2017-03-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Multilayer sheet
KR101866526B1 (en) * 2015-09-17 2018-06-14 주식회사 휴비스 Meta aramid paper with high basis weight

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5076887A (en) * 1990-09-25 1991-12-31 E. I. Du Pont De Nemours And Company Pressboard and process for its production
US5089088A (en) * 1991-02-28 1992-02-18 E. I. Du Pont De Nemours And Company Low-density, high strength aramid boards
WO1994016142A1 (en) * 1993-01-04 1994-07-21 Mishima Paper Co., Ltd. Aramid paper with high surface smoothness

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9517549A1 *

Also Published As

Publication number Publication date
JP3673277B2 (en) 2005-07-20
EP0736120B1 (en) 1998-01-21
DE69408170D1 (en) 1998-02-26
JPH09506938A (en) 1997-07-08
DE69408170T2 (en) 1998-08-20
WO1995017549A1 (en) 1995-06-29
RU2125131C1 (en) 1999-01-20
UA37254C2 (en) 2001-05-15
ES2111394T3 (en) 1998-03-01

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