EP0364629B1 - Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation - Google Patents

Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation Download PDF

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Publication number
EP0364629B1
EP0364629B1 EP88202356A EP88202356A EP0364629B1 EP 0364629 B1 EP0364629 B1 EP 0364629B1 EP 88202356 A EP88202356 A EP 88202356A EP 88202356 A EP88202356 A EP 88202356A EP 0364629 B1 EP0364629 B1 EP 0364629B1
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EP
European Patent Office
Prior art keywords
paper product
paper
structured
latex
particle
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.)
Revoked
Application number
EP88202356A
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German (de)
English (en)
Other versions
EP0364629A1 (fr
Inventor
Medardo Monzon
Michele Renee Lock
James G. Galloway
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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Filing date
Publication date
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Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to EP88202356A priority Critical patent/EP0364629B1/fr
Priority to AT88202356T priority patent/ATE101887T1/de
Priority to DE88202356T priority patent/DE3887988D1/de
Publication of EP0364629A1 publication Critical patent/EP0364629A1/fr
Application granted granted Critical
Publication of EP0364629B1 publication Critical patent/EP0364629B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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Classifications

    • 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
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • 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
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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
    • 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
    • D21H21/22—Agents rendering paper porous, absorbent or bulky

Definitions

  • this invention is directed toward a method for preparing high quality lightweight paper having increased opacity.
  • the method employs a structured latex having both reinforcing and opacifying characteristics.
  • opacity In the manufacture of papers, especially lightweight paper, a major concern is the opacity of the paper. Generally, opacity is provided by conventional fillers such as clay, calcium carbonate and titanium dioxide. Unfortunately, these fillers can adversely affect the mechanical properties of the paper if too much filler is attempted to be incorporated to obtain the desired opacity.
  • US-A-3.897,300 describes a paper filled with a blushed particulate polystyrene pigment filler.
  • This filler consists essentially of spherical particles having an air-containing microporous structure. It is capable of increasing the opacity of a sheet of paper.
  • US-A-4,134,872 relates to a paper product, which is coated with a layer comprising structured latex particles as a binder. These coating layers provide coated paper products having better gloss, ink receptivity, smoothness, wet binding strength, and dry binding strength.
  • US-A-4,613,633 relates to a copolymer latex comprising heterogeneous polymer particles having a hard and a soft polymer domain. These particles are used in paper coating layers.
  • the present invention provides for a structured latex particle suitable for use in the preparation of latex-containing products to increase opacity and strength comprising a core portion having a light scattering characteristic and a T g of 80°C or greater, and a shell portion having a T g of 25°C or lower.
  • the structured latex particles have a particle size of 1,400 to 4,000 angstroms (140 to 400 nm).
  • the structured latex particle has a homopolymer core portion of styrene and a shell region of styrene/butadiene/acrylic acid.
  • the present invention further provides for a paper product prepared with the structured latex particle as described above as a filler in the bulk.
  • the latex particle is employed in the preparation of light weight paper where good opacity and mechanical strength are desired.
  • the subject structured latex particle characteristically provides opacity and reinforcement which allows for the reduction of fillers, such as TiO2, in the article of manufacture. That is, the structured latex particle allows for the reduction or elimination of expensive opacifying fillers in products without a corresponding loss of opacity.
  • Preparation of the products of the present invention requires a starting latex comprising a structured latex particle having a core/shell morphology wherein the core region has a second order transition temperature (T g ) of 80°C or greater and the shell region has a T g of 25°C or lower.
  • T g second order transition temperature
  • the subject latex is employed in the preparation of light weight papers where good opacity and mechanical strength are desired.
  • opaque is meant to define that quality of resisting the passage of light by being neither transparent nor translucent.
  • the opaque characteristic is measurable by measuring the brightness of reflected light, light scattering or reflectance, and opacity (TAPPI standard T-425 om 81).
  • mechanical strength is meant the quality of tensile strength, modulus, tear strength, and other physical properties generally recognized in the art as contributing to mechanical strength.
  • particles of a starting latex are encapsulated with additional monomers polymerized therewith. This can be conveniently accomplished by emulsion polymerizing the desired shell portion monomers in the presence of an existing latex which has the desired core composition.
  • the polymerization is a conventional emulsion polymerization of a latex but for the polymerization of the shell monomer portion being conducted in the presence of a preexisting latex particle which represents the core region of the final latex product.
  • Emulsion polymerization techniques such as staged or continuous addition of monomer feeds are typically employed. Examples of such techniques are further described in U.S. Patent Nos. 4,156,669 and 4,017,442.
  • the structured latex particle of the subject invention requires a core region which has light scattering properties.
  • this light scattering characteristic is provided by a polymer or copolymer of ethylenically unsaturated monomers having a T g of 80°C or greater.
  • the T g of the core region is important in maintaining the identity, i.e., size and distribution, of the core which thereby contributes to the light scattering characteristic of the latex. Contrarily a lower T g would allow the core region to coalesce during paper making and result in a low light scattering characteristic.
  • Difunctional monomers typically useful as crosslinkers, can be employed in the core region to increase the T g of the core region.
  • Examples of good crosslinkers would include allyl or crotyl acrylate and methacrylates and divinyl benzene.
  • the preferred polymer core composition is a monovinyl aromatic polymer such as styrene and copolymers or derivatives thereof having a T g of 80°C or greater. More preferably, the core region is a homopolymer of styrene.
  • the core portion of the structured latex particle comprises from 40 to 90 percent of the total particle.
  • the core/shell polymer weight ratio is from 50/50 to 90/10, respectively.
  • the particle size of the subject structured latex is important to the overall light scattering properties and, therefore, a particle size of from 1,400 to 4,000 angstroms ( ⁇ ) (140 to 400 nm) is preferred. More preferably, the average particle diameter is from 2,000 to 3,500 ⁇ (200 to 350 nm).
  • the shell region of the subject structured latex particle is composed of a polymer or copolymer of ethylenically unsaturated monomers having a T g of 25°C or lower.
  • the shell composition may include monomers employed in the core region.
  • the shell compositions advantageously employed are various blends of polymerized monomers such as monovinyl aromatics, aliphatic conjugated dienes, monoethylenically unsaturated carboxylic acids, vinyl or vinylidene halides or acrylates.
  • reactive monomers such as N-methylolacrylamide and glycidylmethacrylate can be included.
  • monovinyl aromatic monomer is meant to include those monomers with a radical of the formula (wherein R is hydrogen or a lower alkyl such as an alkyl having from 1 to 4 carbon atoms) attached directly to an aromatic nucleus containing from 6 to 10 carbon atoms, including those wherein the aromatic nucleus is substituted with alkyl or halogen substituents.
  • R is hydrogen or a lower alkyl such as an alkyl having from 1 to 4 carbon atoms
  • the preferred monomer is styrene.
  • aliphatic conjugated diene is meant to include compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl- 1,3-butadiene, 2-neopentyl-1,3-butadiene, piperylene (1,3-pentadiene), and other hydrocarbon analogs of 1,3-butadiene.
  • monoethylenically unsaturated carboxylic acid monomer is meant to include those monocarboxylic monomers such as acrylic acid, and methacrylic acid; dicarboxylic monomers such as itaconic acid, fumaric acid, maleic acid, and their monoesters.
  • the preferred acid monomer is acrylic acid.
  • Vinylidene halides and vinyl halides suitable for this invention include vinylidene chloride and vinyl chloride, which are preferred. Vinylidene bromides and vinyl bromide can also be employed.
  • acrylate is meant to include monomers of the acrylate or methacrylate type. Additionally, the acrylates can include acids, esters, amides and substituted derivatives thereof. Generally, the preferred acrylates are C1-C8 alkyl acrylates or methacrylates. Examples of such acrylates include butyl acrylate, 4-biphenyl acrylate, hexyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methylmethacrylate, butylmethacrylate, lauryl methacrylate, hexylmethacrylate, isobutylmethacrylate, and isopropylmethacrylate.
  • the shell region is preferably composed of a polymer blend comprising styrene, butadiene and acrylic acid. This particular blend has been found to yield desirable physical properties and compatibility with the preferred core composition of styrene. Generally, the shell composition has the following styrene/butadiene/acrylic acid ratios of 49/49/2 to 47/47/6; 49/49/2 to 69/29/2; and 69/29/2 to 67/27/6, respectively.
  • Structured latex particles prepared in the foregoing manner are advantageously employed as paper coatings or fillers where good opacity and mechanical properties are desirable. More particularly, paper products prepared with the subject structured particle latex will have increased opacity and strength over a similar paper prepared in the absence of the structured particle latex. While not limited to paper applications, the subject latex can also be employed as a filler or component in other areas where latexes may be employed such as in protective or decorative coatings, e.g., paints, etc. More advantageously, the subject structured latexes are employed as a latex binder or as a partial substitute for the latex binder in the preparation of high quality lightweight or fine papers. Lightweight papers are generally defined as those papers having less than 34 pounds/3300 sq.ft. or approximately 50 g/sq.meter.
  • a structured latex was prepared in the following manner. To 80 parts by weight per 100 parts comonomer charge of an aqueous medium containing .01 part by weight of a pentasodium salt of diethylenetriaminepentacetic acid and 0.52 part by weight of a 97/3 weight ratio styrene/acrylic acid copolymer seed latex was continuously added 100 parts by weight of a styrene monomer feed with stirring over a period of 2.8 hours.
  • aqueous stream containing 40 parts deionized water, 1.0 part by weight of sodium dodecyldiphenyl ether disulfonate, 0.5 part by weight of sodium persulfate and 0.1 part by weight of sodium hydroxide was added with said styrene feed for a period of 4.5 hours at 90°C.
  • a 49/49/2 weight ratio of styrene/butadiene/acrylic acid comonomer feed was continuously added with stirring over a 1.2 hour period.
  • the comonomer feed also contained 0.15 part by weight of tertiary dodecylmercaptan.
  • the resulting latex had a total solids content of about 43 percent, a pH of 3, and the structured latex particles had an average particle diameter of 1550 ⁇ (155 nm), and a polystyrene core (T g approximately 100°C) to styrene/butadiene/acrylic acid shell (T g lower than 25°C) ratio of 70/30.
  • a structured latex particle was prepared as in Example 1 except that the core/shell ratio was 50/50.
  • Paper compositions employing the latexes prepared in Examples 1 and 2 as reinforcing opacifiers were prepared. Seven and one-half parts (polymer solids basis) of the latexes from Examples 1 and 2 were admixed with individual samples of an aqueous paper composition.
  • the paper composition consisted of 6,424 parts of an aqueous suspension containing 92.5 parts (dry weight basis) of bleached kraft wood fibers (50/50 dry weight ratio of hardwood/softwood), 100 parts of a 2 percent by weight aqueous solution of aluminum sulfate octadecahydrate, and 3.5 parts of 0.1 percent by weight aqueous solution of a high molecular weight polyacrylamide.
  • the suspensions described above were used to form paper handsheets having a basis weight of 40 lbs./3300 sq.ft. (59.2 g/m2)on a Noble and Wood paper machine.
  • the structured particle latex content of each paper was measured by pyrolysis-gas chromatography.
  • the opacity, brightness, tensile strength and elongation of the handsheets were measured and are shown below with a comparative paper example prepared as above except in the absence of the structured latex particles of this invention.
  • the subject structured latex particle can comprise from 1 to 20 percent by dry weight basis of the paper composition.
  • the latex content of the paper is from 2 to 10 percent by weight.

Landscapes

  • Paper (AREA)
  • Graft Or Block Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (10)

  1. Produit à base de papier, de faible poids, contenant, comme charge dans la masse, des particules de latex structurées, comprenant :
    (1) une partie coeur ayant des propriétés de diffusion de la lumière et une Tg supérieure ou égale à 80°C, et
    (2) une partie enveloppe ayant une Tg inférieure ou égale à 25°C,
       grâce à quoi l'opacité et la résistance dudit papier sont augmentées par rapport à celles d'un produit à base de papier, préparé en l'absence desdites particules de latex structurées.
  2. Produit à base de papier selon la revendication 1, dans lequel les particules de latex structurées représentent de 1 à 20 % en poids à l'état sec dudit papier.
  3. Produit à base de papier selon la revendication 1, pour lequel ladite partie coeur comprend un polymère aromatique monovinylique, un copolymère ou un dérivé des précédents.
  4. Produit à base de papier selon la revendication 3, pour lequel ledit polymère aromatique monovinylique est un polymère de styrène.
  5. Produit à base de papier selon la revendication 1, dans lequel lesdites particules de latex structurées présentent une région coeur, constituée d'un homopolymère de styrène.
  6. Produit à base de papier selon la revendication 3, pour lequel ladite partie coeur renferme en plus des monomères bifonctionnels qui contribuent à l'augmentation de la Tg dudit coeur.
  7. Produit à base de papier selon la revendication 6, pour lequel ledit monomère bifonctionnel comprend les acrylates et/ou méthacrylates d'allyle ou de crotyle, ou le divinylbenzène.
  8. Produit à base de papier selon la revendication 1, dans lequel lesdites particules de latex structurées présentent une région enveloppe comprenant un mélange polymère de styrène/butadiène/acide acrylique.
  9. Produit à base de papier selon la revendication 8, pour lequel le rapport styrène/butadiène/acide acrylique dudit mélange polymère est 49/49/2 à 47/47/6, 49/49/2 à 69/29/2, et 69/29/2 à 67/27/6, respectivement.
  10. Procédé de préparation d'un produit à base de papier, de faible poids, contenant, comme charge dans la masse, des particules de latex structurées, qui comprend :
    (a) la fourniture de particules de latex structurées, comprenant :
    (1) une partie coeur ayant des propriétés de diffusion de la lumière et une Tg supérieure ou égale à 80°C, et
    (2) une partie enveloppe ayant une Tg inférieure ou égale à 25°C,
    (b) le mélange desdites particules de latex structurées avec une composition aqueuse de papier, et
    (c) la mise du mélange sous la forme d'un papier.
EP88202356A 1988-10-21 1988-10-21 Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation Revoked EP0364629B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP88202356A EP0364629B1 (fr) 1988-10-21 1988-10-21 Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation
AT88202356T ATE101887T1 (de) 1988-10-21 1988-10-21 Papierprodukt, hergestellt mit strukturierten latexteilchen mit verstaerkenden und opaken eigenschaften und verfahren zu seiner herstellung.
DE88202356T DE3887988D1 (de) 1988-10-21 1988-10-21 Papierprodukt, hergestellt mit strukturierten Latexteilchen mit verstärkenden und opaken Eigenschaften und Verfahren zu seiner Herstellung.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88202356A EP0364629B1 (fr) 1988-10-21 1988-10-21 Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation

Publications (2)

Publication Number Publication Date
EP0364629A1 EP0364629A1 (fr) 1990-04-25
EP0364629B1 true EP0364629B1 (fr) 1994-02-23

Family

ID=8199872

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88202356A Revoked EP0364629B1 (fr) 1988-10-21 1988-10-21 Produit papetier préparé avec des particules de latex structurées améliorant la solidité et l'opacité, et procédé de préparation

Country Status (3)

Country Link
EP (1) EP0364629B1 (fr)
AT (1) ATE101887T1 (fr)
DE (1) DE3887988D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19525736A1 (de) * 1995-07-14 1997-01-16 Huels Chemische Werke Ag Verstärkte Kautschukdispersion, ihre Herstellung und Verwendung
JPH0987993A (ja) * 1995-09-21 1997-03-31 Rohm & Haas Co 無塵紙
AU2697899A (en) * 1998-05-18 1999-11-25 Rohm And Haas Company Hollow sphere organic pigment for paper or paper coatings
US9206552B2 (en) 2012-02-17 2015-12-08 International Paper Company Absorbent plastic pigment with improved print density containing and recording sheet containing same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897300A (en) * 1971-11-05 1975-07-29 Westvaco Corp Paper filled with a blushed particulate polystyrene pigment
US4282060A (en) * 1977-06-03 1981-08-04 Hercules Incorporated Organic pigments
JPS6045696A (ja) * 1983-08-22 1985-03-12 日本ゼオン株式会社 紙塗被組成物

Also Published As

Publication number Publication date
DE3887988D1 (de) 1994-03-31
EP0364629A1 (fr) 1990-04-25
ATE101887T1 (de) 1994-03-15

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