EP0357933B1 - Schlagfeste Schmelzklebstoffzusammensetzung für Buchscharnierverbindungen - Google Patents

Schlagfeste Schmelzklebstoffzusammensetzung für Buchscharnierverbindungen Download PDF

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Publication number
EP0357933B1
EP0357933B1 EP19890113801 EP89113801A EP0357933B1 EP 0357933 B1 EP0357933 B1 EP 0357933B1 EP 19890113801 EP19890113801 EP 19890113801 EP 89113801 A EP89113801 A EP 89113801A EP 0357933 B1 EP0357933 B1 EP 0357933B1
Authority
EP
European Patent Office
Prior art keywords
hot melt
weight
book
resins
adhesive composition
Prior art date
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Expired - Lifetime
Application number
EP19890113801
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English (en)
French (fr)
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EP0357933A1 (de
Inventor
Thomas P. Flanagan
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.)
National Starch and Chemical Investment Holding Corp
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National Starch and Chemical Investment Holding Corp
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Publication of EP0357933A1 publication Critical patent/EP0357933A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42C—BOOKBINDING
    • B42C9/00—Applying glue or adhesive peculiar to bookbinding

Definitions

  • the present invention is directed to toughened pressure sensitive hot melt adhesives used to form the hinge joint of a flexible covered book.
  • Flexible or soft covered books are generally formed by coating a layer of hot melt adhesive on the secured edge of a series of printed stocks or signatures to form a book block to which a paper backing or other suitable cover is applied to form the spine of the book. While this process produces the primary bonding of the book block to the cover, a secondary bond is often formed at the hinge or joint of the cover. This bond is produced by applying a small amount of adhesive to the outer sheet of each side of the book block immediately adjacent to the hinge area. This hinge joint formation is actually carried out in two separate steps with the adhesive being applied to the book block before the cover is affixed and the joint then being formed by application of pressure to the book cover at some point "downline" in the manufacturing operation. The purpose of this adhesive application is to conceal the binding adhesive and also to reinforce the binding and to prevent the book from falling apart relatively easily when grasped only by the flexible cover.
  • the adhesives used for this application must possess a variety of properties, specifically they must possess low viscosity (i.e., about 500 to 5000 mPa.s at 176.67°C (500 to 5000 cps at 350°F)) for easy application, strong agressive tack at the point of formation of the hinge bond, good adhesion to difficult cover stocks and resistance to creep or cold flow both at room temperature and under elevated temperature conditions.
  • the adhesives used have generally been either the non-pressure sensitive hot melt adhesives used in the book binding operation or emulsion adhesives. Both types of adhesives suffer from the common deficiency of their relatively short open time i.e., the time during which a bond may be found.
  • US-A-4 712 808 discloses a process for the formation of the hinge joints on bound book blocks using a hot melt pressure sensitive adhesive comprising: a) 20 to 35% by weight of an A-B-A block or A-B-A-B-A-B mulit-block copolymer where the A component is styrene and the B component is butadiene or hydrogenated butadiene and the copolymer contains at least 28 parts styrene per 100 parts copolymer; b) 45 to 70% by weight of a compatible tackifying resin; c) 5 to 30% by weight of a plasticizing oil; d) 0 to 5% by weight of a petroleum derived wax; and e) 0.1 to 2% by weight of a stabilizer.
  • pressure sensitive hot melt adhesive compositions prepared adhesives which comprise a substantially radial styrene-butadiene block copolymer, the copolymer having a styrene content greater than about 35% by weight, a modulus at 300% elongation of at least 4.5 MPa and a solution viscosity less than about 1000 mPa.s (1000 cps) are particularly useful in the formation of hinge joints for flexible books.
  • the present invention is directed to a process for the formation of hinge joints on bound book blocks comprising the steps of applying a molten film of a hot melt pressure sensitive adhesive to the outer sheet of each side of the book block on an area immediately adjacent the bound edges and for a length substantially coterminus with the bound edges; applying a cover thereto; and exerting pressure on the book cover in the area of the pressure sensitive hot melt film; wherein the pressure sensitive hot melt adhesive comprises:
  • the block copolymers useful herein are comprised of styrene and butadiene blocks arranged in a substantially radial configuration and contain at least 35%, and generally up to about 50%, by weight of the styrene moiety. Of greater significance however, the copolymers selected should exhibit a modulus at 300% elongation of at least about 4.5 MPa and a solution viscosity less than about 1000 mPa.s (1000 cps) (25% in toluene at 23°C using a Brookfield viscometer). These copolymers may be prepared using methods taught, for example, in US-A-3,239,478; 3,427,269; 3,700,633; 3,753,936 and 3,932,327.
  • the tackifying resins useful in the adhesive compositions can be hydrocarbon resins, hydrogenated hydrocarbon resins, synthetic polyterpenes, rosin esters, natural polyterpenes, and the like. More particularly, the useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modified rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural and modified rosins, such, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerised rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) cop
  • the remainder (up to about 60% by weight) of the hot melt adhesive comprises at least one oil diluent.
  • Suitable plasticizing or extending oils include not only the usual plasticizing oils but also olefin oligomers and low molecular weight polymers as well as vegetable and animal oil and their derivatives.
  • the petroleum derived oils which may be employed are relatively high boiling materials containing only a minor proportion of aromatic hydrocarbons (preferably less than 30% and, more particularly, less than 15% by weight of the oil). Alternatively, the oil may be totally non-aromatic.
  • the oligomers may be polypropylenes, polybutenes, hydrogenated polyisoprene, hydrogenated polybutadiene, or the like having average molecular weights between 350 and 10,000.
  • hindered phenols include high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-containing phenols.
  • Hindered phenols are well known to those skilled in the art and may be characterized as phenolic compounds which also contain sterically bulky radicals in close proximity to the phenolic hydroxyl group thereof.
  • tertiary butyl groups generally are substituted onto the benzene ring in at least one of the ortho positions relative to the phenolic hydroxy group.
  • hindered phenols include: 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene; pentaerythrityl tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4'-methylenebis (2,6-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,6-di-tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)
  • Optional additives may be incorporated into the hot melt compositions in order to modify certain properties thereof.
  • these additives may be included colorants such as titanium dioxide; and fillers such as talc and clay, etc. as well as minor amounts (e.g. less than about 5%) of a petroleum derived wax.
  • hot melt adhesive compositions may be formulated using techniques known in the art.
  • An exemplary procedure involves placing approximately half of the total tackifying resin concentration in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer of the Baker-Perkins or Day type, which is equipped with rotors and thereupon raising the temperature to a range of from 121.11 to 176.67°C (250° to 350°F.), the precise temperature utilized depending on the melting point of the particular tackifying resins.
  • stirring is initiated and the block polymer and stabilizer are added together with any optional additives whose presence may be desired, the addition of the latter components being extended over a prolonged period in order to avoid the formation of lumps.
  • the resultant hot melt adhesives are generally produced with an oil in bulk form and packaged in release coated tube or boxes.
  • Adhesives were prepared from the materials and amounts shown in Table I using the general procedure described above. Viscosity measurements were determined using a Brookfield viscometer (Spindle 27) at 162.78 (325°F). The adhesives were subjected to the following tests to determine the heat resistance of the adhesive under a constant load and static stress and elevated temperature.
  • the adhesive was heated to 160°C (320°F) and a lamination of kraft paper was made using heated rollers.
  • the adhesive thickness was 1.27 mm (50 mil) and the bonds having an adhesive area of one square inch.
  • the bonds were aged overnight at 22.22°C (72°F) and 50% RH.
  • the peel mode samples were then hung in a 40.56°C (105°F) oven using 118g/cm. (300 gram/inch weights). The time at which the bond failed was noted as was the mode of failure.
  • the tensile strength of the hot melt adhesive was determined on samples cast from the hot melts and molded in silicone rubber molds into the shape of dog bones . After cooling, the dog bone shaped specimens were removed from the mold and tested using an Instron Tensile Tester. The force required to start to stretch the specimen is recorded as the "tensile yield", the force required to break the specimen as "tensile break”. This procedure also provides a measurement of percent elongation, which is the percentage stretch of the hot melt sample at the point of rupture in obtaining the ultimate tensile strength. The testing results of Samples 1-8 show significantly higher ultimate tensile strength of the adhesives of the present invention when contrasted with presently commercially utilized adhesive compositions containing similar amounts of raw materials.
  • Sample 9 shows that it is possible to use less polymer to obtain a lower viscosity adhesive without sacrifice of tensile strength. (Compare to Sample 11 prepared with 15 parts Stereon). Note however the product did suffer with respect to Kraft/Kraft adhesive and hence would not be readily useful for certain end use applications where stringent heat resistance values are required.
  • Samples 12, 13 and 14 show results similar to those of Sample 9, additionally overcoming the deficiency of Sample 9 with respect to heat resistance by use of a different tackifier system.
  • Sample 17 shows a further formulation according to the invention using a different tackifying system. Note, in particular, the high heat resistance value.
  • Samples 18 through 26 again shown the improved heat resistance and ultimate tensile strength achieved using adhesive compositions of the invention as contrasted to conventionally employed Stereon containing adhesive systems with Samples 24, 25 and 26, also showing that lower levels of the Kraton D1122X may be used to obtain lower viscosity products without sacrifice to the tensile strength.
  • the resultant adhesives may be used to form the hinge joint using methods conventional in the book binding art and without limitation to the particular binding method employed.
  • the book block may be bound by any of the usual procedures, including, but not limited to, perfect binding with hot melt adhesive, burst binding with emulsion adhesive and then with hot melt adhesive; sewn and glued off with emulsion adhesive; or perfect or burst bound with emulsion adhesive.
  • a film of a non-pressure sensitive adhesive is coated on the secured edges of the book block; then a molten film of the hot melt pressure sensitive adhesive described previously is coated on the outer sheet of each side of the book block on an area immediately adjacent the secured edges and for a length substantially coterminus therewith; the flexible cover is applied to the first film while the latter is still in the uncured state and pressure is exerted on the book cover in the area of the pressure sensitive hot melt film to form the hinge joint.
  • the hinge or joint hot melt may be applied in appropriate lines to the flexible cover as the cover is fed on the binder to next to the book block.

Landscapes

  • Adhesives Or Adhesive Processes (AREA)

Claims (3)

  1. Verfahren zur Bildung von Scharnierverbindungen bei gebundenen Buchblöcken, umfassend die Schritte von: Aufbringen eines geschmolzenen Filmes eines Heißschmelzklebstoffes auf den äußeren Bogen jeder Seite des Buchblockes auf ein unmittelbar an die gebundenen Kanten angrenzendes Gebiet und für eine Länge, die im wesentlichen mit den gebundenen Kanten übereinstimmt; Aufbringen eines Einbandes darauf und Anwenden von Druck auf den Bucheinband in dem Gebiet des Heißschmelzfilmes, worin der Heißschmelzklebstoff ein druckempfindlicher Heißschmelzklebstoff ist, der umfaßt:
    a) 10 bis 40 Gew.-% eines im wesentlichen radialen Styrol-Butadien-Blockcopolymers, das einen Styrolgehalt größer als etwa 35 Gew.-%, einen Modul bei 300 % Dehnung von mindestens 4,5 MPa und eine Lösungsviskosität von weniger als etwa 1000 mPa.s (1000 cps) aufweist,
    b) 20 bis 65 Gew.-% eines kompatiblen klebrigmachenden Harzes,
    c) 0,1 bis 4 Gew.-% Stabilisator,
    d) wobei der Rest bis zu etwa 60 Gew.-% ein plastifizierendes Öl umfaßt.
  2. Verfahren nach Anspruch 1, worin der Klebrigmacher in der druckempfindlichen Heißschmelzklebstoffzusammensetzung jedes kompatible Harz oder eine Mischung davon ist, ausgewählt aus der Gruppe, bestehend aus (1) natürlichen und modifizierten Naturharzen, (2) Glycerol- und Pentaerythritolestern natürlicher und modifizierter Naturharze, (3) Copolymeren und Terpolymeren natürlicher Terpene, (4) Polyterpenharzen mit einem Erweichungspunkt, bestimmt nach dem ASTM-Verfahren E28-58T, von etwa 80 bis 150°C, (5) phenolmodifizierten Terpenharzen und hydrierten Derivaten davon, (6) aliphatischen Erdölkohlenwasserstoffharzen mit einem Kugel- und Ringerweichungspunkt von etwa 70 bis 135°C, (7) aromatischen Erdölkohlenwasserstoffharzen und den hydrierten Derivaten davon und (8) alicyclischen Erdölkohlenwasserstoffharzen und den hydrierten Derivaten davon.
  3. Buch, hergestellt nach dem Verfahren von Anspruch 1.
EP19890113801 1988-08-17 1989-07-26 Schlagfeste Schmelzklebstoffzusammensetzung für Buchscharnierverbindungen Expired - Lifetime EP0357933B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23317588A 1988-08-17 1988-08-17
US233175 1999-01-19

Publications (2)

Publication Number Publication Date
EP0357933A1 EP0357933A1 (de) 1990-03-14
EP0357933B1 true EP0357933B1 (de) 1993-10-20

Family

ID=22876199

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890113801 Expired - Lifetime EP0357933B1 (de) 1988-08-17 1989-07-26 Schlagfeste Schmelzklebstoffzusammensetzung für Buchscharnierverbindungen

Country Status (5)

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EP (1) EP0357933B1 (de)
JP (1) JPH0717884B2 (de)
CA (1) CA1336950C (de)
DE (1) DE68910060T2 (de)
DK (1) DK402889A (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19956134C2 (de) * 1999-11-23 2003-04-03 Daimler Chrysler Ag Mit Kraftstoffeinspritzung und Fremdzündung arbeitende, ventilgesteuerte Hubkolben-Brennkraftmaschine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950291A (en) * 1974-06-03 1976-04-13 Phillips Petroleum Company Hot-melt adhesive composition
US4712808A (en) * 1986-02-19 1987-12-15 National Starch And Chemical Corporation Hot melt adhesive composition for book hinge joint
US4722650A (en) * 1986-02-19 1988-02-02 National Starch And Chemical Corporation Hot melt adhesive composition for book casemaking
US4660858A (en) * 1986-02-20 1987-04-28 National Starch And Chemical Corporation Hot melt adhesive composition for book lining

Also Published As

Publication number Publication date
JPH0717884B2 (ja) 1995-03-01
CA1336950C (en) 1995-09-12
DK402889A (da) 1990-02-18
DE68910060T2 (de) 1994-03-10
DK402889D0 (da) 1989-08-16
EP0357933A1 (de) 1990-03-14
JPH0291181A (ja) 1990-03-30
DE68910060D1 (de) 1993-11-25

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