CA1178734A - Adhesive for perfect bound books and method of using same - Google Patents
Adhesive for perfect bound books and method of using sameInfo
- Publication number
- CA1178734A CA1178734A CA000396605A CA396605A CA1178734A CA 1178734 A CA1178734 A CA 1178734A CA 000396605 A CA000396605 A CA 000396605A CA 396605 A CA396605 A CA 396605A CA 1178734 A CA1178734 A CA 1178734A
- Authority
- CA
- Canada
- Prior art keywords
- vinyl acetate
- composition
- moieties
- book
- block
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42C—BOOKBINDING
- B42C9/00—Applying glue or adhesive peculiar to bookbinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Hot melt adhesives especially suited for use in the-perfect bind-ing of books are prepared from (1) 15-30%X of a block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a nonvinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moities of a conjugated diene monomer;
(2) 5-10% of an ethylene vinyl acetate copolymer containing 17 to 42% vinyl acetate; wherein the ratio of the block polymer to the ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins.
(4) 25-35% of a wax diluent which is solid at room temperature:
and (5) 0,5 to 3% of at least one stabilizer.
The novel adhesives can be applied to coated stock which has not been primed, and they combine good application properties with the desirable book properties of "easy opening" and good "cold-crack".
Hot melt adhesives especially suited for use in the-perfect bind-ing of books are prepared from (1) 15-30%X of a block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a nonvinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moities of a conjugated diene monomer;
(2) 5-10% of an ethylene vinyl acetate copolymer containing 17 to 42% vinyl acetate; wherein the ratio of the block polymer to the ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins.
(4) 25-35% of a wax diluent which is solid at room temperature:
and (5) 0,5 to 3% of at least one stabilizer.
The novel adhesives can be applied to coated stock which has not been primed, and they combine good application properties with the desirable book properties of "easy opening" and good "cold-crack".
Description
7~73~
IMPROVED ADHESIVE FOR PERFECT BOUND BOOKS
AND METHOD OF USING SAME
The "perfect" binding of books with hot melt adhesives is a high speed, continuous operation used in the book-binding industry for the binding of paper-back books, catalogs, magazines, etc. In this operation, the books are printed in sheets or long continuous webs which are cut, folded and properly arranged to form a series of stacks, referred to as signatures, which are then fed into a revolv-ing mechanism equipped with clamps. The folded edges of the clamped sheets are first cut to remove the signature folds, and then the edges of the sheets are roughened so as to expose a maximum amount of fibers and thereby render them more receptive to the hot melt adhesive composition. A layer or coat of the molten adhesive composition is then applied by means of a suitable applicator, after which a paper backing or other suitable cover is applied before the molten adhesive sets to form the spine of the book. The perfect bound book is then trimmed to the desired size, and optionally the exposed sheet edges are colored as by painting or dyeing to give the finished product.
Hot melt adhesive compositions useful for the perfect binding of books serve at least two critical functions. In the first place, they must hold the book together during its formation. Thus, it is necessary that they be capable of forming thin films in the molten state; that they wet rapidly; that they have good tack or adhesion for similar and .~.
dissimilar sheets ranging from coated paper, enameled stock, cross and long grain, coated or uncoated sheets, groundwood or sulfite;
that they be quick setting but not so quick as to prevent the cover from bonding; and that they be capable of exhibiting a required range of viscosities in order to be applicable for use with any available and generally suitable hot melt applicator. Secondly, on cooling or setting, the hot melt adhesive must be able to produce spines having good "wear potential" so as to be capable of preventing the book from falling apart. Wear potential includes the properties of high bond-ing strength, flexibility, high film strength (tensile strength) andresistance to aging, mold growth, and "cold crack." "Cold crack" is the undesirable hardness of the spine which prevents the opening of a book to 360, i.e. so that the covers are back-to-back to one another, without causing the spine to split. This characteristic is dependent upon temperature and is of particular importance when books are exposed to cold climates. Since the perfect bound book has no staples, threads, stitches, etc., cracking of the spine causes the book to split.
An additional requirement of rnany publishers is the feature that the book or magazine be "easy-opening", i.e., that the two-page spread may be completely opened and will remain in the open position when placed down, as on a table or the like. This characteristic is in direct contrast to the behavior exhibited by conventional stiff paper-back books which will snap closed as soon as they are placed down (known in the trade as "mousetrapping"~. These books can normally be kept open only by exerting pressure directly on the spine so as to loosen, break or crack the adhesive binding.
~i7~'7;~ ~
The conventional adhesives are often limited in their effective-ness as hot melts for the perfect binding of books because they are only mediocre with regard to one or more of the properties enumerated above. Often it has been necessary to compromise certain properties in order to obtain products having at least a narrow range of useful properties. Thus, for example, hot melts based on polyvinyl acetate have shown poor warm flow (i.e. undesirable softness) and high cold crack characteristics. In addition, hot melts based on ethylene-vinyl acetate copolymer systems have experienced various adhesive problems and the books which have been bound with the latter hot melts have exhibited poor "easy-opening" properties. U.S. Pat. No. 3,837,994 issued September 24, 1974 to T. P. Flanagan et. al. teaches a hot melt adhesive which overcomes the previously described problems but which has been found to be limited in its commercial applicability due to a primer step being required when the adhesive is to be used on coated stock in conjunction with the high speed equipment found in the many operating plants. The use of this primer in order to obtain superior properties is a drawback, particularly in the case of magazines which are issued weekly where, in order to maintain the large scale production and widespread circulation requirements, multiple plants (often with multiple lines) are simultaneously run.
It will be appreciated that the multiplication of equipment required if primers are to be used (primer applicators, etc.) is constrained both from an economic as well as a physical limitation.
The present invention provides a method for the perfect binding of books which does not require the use of a primer even for coated stocks. It also provides a method which does not require the user to compromise any of the useful characteristics and especially the easy opening and cold crack characteristics. It further provides a novel hot melt adhesive for use in such a process.
As can be seen from the above, a hot melt adhesive providing the above features must be formulated within very precise boundaries in order to obtain the necessary balance of properties. Therefore, in preparing such adhesive compositions, the following properties tend to be critical:
Fast set: When used without the primer, the hot melt compositions of U.S. Pat. No. 3,837,994 (cited hereinabove) capable of bonding coated papers possess setting speeds which are generally too slow for use on machines running at speeds greater than about 180 clamps per minute reaching the trimmer in 30-35 seconds. This slow setting speed causes gumming of the machine parts in the trimming operation with the uncured adhesive stringing and smearing on the edges of the bound and trimmed book. The adhesive herein must therefore cure (set-up~ within 30 seconds, preferably within 26 seconds, frorn the time it was applied while still providing adequate adhesion.
Viscosity: In order to function on the machines utilized, it is necessary that the adhesive have a melt viscosity within the range of about 3,000 to 30,000 cps at 177C (350F).
Yield strength: The adhesive film itself must have a critical balance in yield strength as measured in accordance with Test Method A
of ASTM Procedure D882-5GT on an Instron Tensile Tester using a separ-ation rate of 50.8 cm./min. (20 in./min.). The yield strength must be sufficently high so as to prevent the page from pulling out when turned but must be low enough to allow for easy opening properties. We have li7~
found that most adhesives based on EVA possess a yield strength too high to be suitable for use where easy opening properties are re-quired. Thus, adhesives formulated herein must have a yield strength of 7.03 to 14.06 kg./cm.2 (100 to 250 psi.).
Low temperature flexibility: The adhesive must exhibit a low temperature flexibility of less than about -12C (10F.), preferably -26 to -32C (-15 to -25F); i.e., no cold crack at such temperatures.
Page pull: Once the book has been formed, it is necessary to ascertain whether the adhesive has sufficient strength to prevent the book from being easily pulled apart. This testing is done using a Page Pull Tester and is referred to as page pull test. The adhesives formulated for use herein must exhibit a page pull of at least 4.5 kg. (10 lb.), preferably at least 6.8 kg. (15 lb.), per page when tested on coated stock (page length about 18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long).
Non-pressure sensitive: A pressure sensitive adhesive is one which remains tacky for prolonged periods (or permanently) after being coated upon a surface. In the perfect binding process utilized herein, the semi-finished books must be trimmed to the desired final size after application of the adhesive. A tacky adhesive (i.e. one that is pressure sensitive) cannot be used for book binding because the adhesive would undesirably accumulate on the knives or blades used in the cutting operation and the random spreading of the adhesive would ruin the books. It is thus essential that the adhesives used in the process herein be non-pressure sensitive.
The invention herein provides a non-pressure sensitive hot melt adhesive composition comprising on a weight basis:
'7;~ ~
(1) 15-30% of at least one block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived fronn the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
IMPROVED ADHESIVE FOR PERFECT BOUND BOOKS
AND METHOD OF USING SAME
The "perfect" binding of books with hot melt adhesives is a high speed, continuous operation used in the book-binding industry for the binding of paper-back books, catalogs, magazines, etc. In this operation, the books are printed in sheets or long continuous webs which are cut, folded and properly arranged to form a series of stacks, referred to as signatures, which are then fed into a revolv-ing mechanism equipped with clamps. The folded edges of the clamped sheets are first cut to remove the signature folds, and then the edges of the sheets are roughened so as to expose a maximum amount of fibers and thereby render them more receptive to the hot melt adhesive composition. A layer or coat of the molten adhesive composition is then applied by means of a suitable applicator, after which a paper backing or other suitable cover is applied before the molten adhesive sets to form the spine of the book. The perfect bound book is then trimmed to the desired size, and optionally the exposed sheet edges are colored as by painting or dyeing to give the finished product.
Hot melt adhesive compositions useful for the perfect binding of books serve at least two critical functions. In the first place, they must hold the book together during its formation. Thus, it is necessary that they be capable of forming thin films in the molten state; that they wet rapidly; that they have good tack or adhesion for similar and .~.
dissimilar sheets ranging from coated paper, enameled stock, cross and long grain, coated or uncoated sheets, groundwood or sulfite;
that they be quick setting but not so quick as to prevent the cover from bonding; and that they be capable of exhibiting a required range of viscosities in order to be applicable for use with any available and generally suitable hot melt applicator. Secondly, on cooling or setting, the hot melt adhesive must be able to produce spines having good "wear potential" so as to be capable of preventing the book from falling apart. Wear potential includes the properties of high bond-ing strength, flexibility, high film strength (tensile strength) andresistance to aging, mold growth, and "cold crack." "Cold crack" is the undesirable hardness of the spine which prevents the opening of a book to 360, i.e. so that the covers are back-to-back to one another, without causing the spine to split. This characteristic is dependent upon temperature and is of particular importance when books are exposed to cold climates. Since the perfect bound book has no staples, threads, stitches, etc., cracking of the spine causes the book to split.
An additional requirement of rnany publishers is the feature that the book or magazine be "easy-opening", i.e., that the two-page spread may be completely opened and will remain in the open position when placed down, as on a table or the like. This characteristic is in direct contrast to the behavior exhibited by conventional stiff paper-back books which will snap closed as soon as they are placed down (known in the trade as "mousetrapping"~. These books can normally be kept open only by exerting pressure directly on the spine so as to loosen, break or crack the adhesive binding.
~i7~'7;~ ~
The conventional adhesives are often limited in their effective-ness as hot melts for the perfect binding of books because they are only mediocre with regard to one or more of the properties enumerated above. Often it has been necessary to compromise certain properties in order to obtain products having at least a narrow range of useful properties. Thus, for example, hot melts based on polyvinyl acetate have shown poor warm flow (i.e. undesirable softness) and high cold crack characteristics. In addition, hot melts based on ethylene-vinyl acetate copolymer systems have experienced various adhesive problems and the books which have been bound with the latter hot melts have exhibited poor "easy-opening" properties. U.S. Pat. No. 3,837,994 issued September 24, 1974 to T. P. Flanagan et. al. teaches a hot melt adhesive which overcomes the previously described problems but which has been found to be limited in its commercial applicability due to a primer step being required when the adhesive is to be used on coated stock in conjunction with the high speed equipment found in the many operating plants. The use of this primer in order to obtain superior properties is a drawback, particularly in the case of magazines which are issued weekly where, in order to maintain the large scale production and widespread circulation requirements, multiple plants (often with multiple lines) are simultaneously run.
It will be appreciated that the multiplication of equipment required if primers are to be used (primer applicators, etc.) is constrained both from an economic as well as a physical limitation.
The present invention provides a method for the perfect binding of books which does not require the use of a primer even for coated stocks. It also provides a method which does not require the user to compromise any of the useful characteristics and especially the easy opening and cold crack characteristics. It further provides a novel hot melt adhesive for use in such a process.
As can be seen from the above, a hot melt adhesive providing the above features must be formulated within very precise boundaries in order to obtain the necessary balance of properties. Therefore, in preparing such adhesive compositions, the following properties tend to be critical:
Fast set: When used without the primer, the hot melt compositions of U.S. Pat. No. 3,837,994 (cited hereinabove) capable of bonding coated papers possess setting speeds which are generally too slow for use on machines running at speeds greater than about 180 clamps per minute reaching the trimmer in 30-35 seconds. This slow setting speed causes gumming of the machine parts in the trimming operation with the uncured adhesive stringing and smearing on the edges of the bound and trimmed book. The adhesive herein must therefore cure (set-up~ within 30 seconds, preferably within 26 seconds, frorn the time it was applied while still providing adequate adhesion.
Viscosity: In order to function on the machines utilized, it is necessary that the adhesive have a melt viscosity within the range of about 3,000 to 30,000 cps at 177C (350F).
Yield strength: The adhesive film itself must have a critical balance in yield strength as measured in accordance with Test Method A
of ASTM Procedure D882-5GT on an Instron Tensile Tester using a separ-ation rate of 50.8 cm./min. (20 in./min.). The yield strength must be sufficently high so as to prevent the page from pulling out when turned but must be low enough to allow for easy opening properties. We have li7~
found that most adhesives based on EVA possess a yield strength too high to be suitable for use where easy opening properties are re-quired. Thus, adhesives formulated herein must have a yield strength of 7.03 to 14.06 kg./cm.2 (100 to 250 psi.).
Low temperature flexibility: The adhesive must exhibit a low temperature flexibility of less than about -12C (10F.), preferably -26 to -32C (-15 to -25F); i.e., no cold crack at such temperatures.
Page pull: Once the book has been formed, it is necessary to ascertain whether the adhesive has sufficient strength to prevent the book from being easily pulled apart. This testing is done using a Page Pull Tester and is referred to as page pull test. The adhesives formulated for use herein must exhibit a page pull of at least 4.5 kg. (10 lb.), preferably at least 6.8 kg. (15 lb.), per page when tested on coated stock (page length about 18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long).
Non-pressure sensitive: A pressure sensitive adhesive is one which remains tacky for prolonged periods (or permanently) after being coated upon a surface. In the perfect binding process utilized herein, the semi-finished books must be trimmed to the desired final size after application of the adhesive. A tacky adhesive (i.e. one that is pressure sensitive) cannot be used for book binding because the adhesive would undesirably accumulate on the knives or blades used in the cutting operation and the random spreading of the adhesive would ruin the books. It is thus essential that the adhesives used in the process herein be non-pressure sensitive.
The invention herein provides a non-pressure sensitive hot melt adhesive composition comprising on a weight basis:
'7;~ ~
(1) 15-30% of at least one block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived fronn the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
(2) 5-10% of at least one ethylene vinyl acetate copolymer containing about 17 to 42% vinyl acetate; the weight ratio of the block polymer to the ethylene vinyl acetate copolymer being within the range of 1.75~1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins,
(4) 25-35% of at least one wax diluent which is solid at room temperature; and
(5) 0.5 to 3% of at least one stabilizer;
said composition being characterized by an ability to form a film exhibiting Instron yield strenyths of 7.03-14.06 kg./cm.2 (100-250 psi.) and a low temperature flexibility of less than -12C (10F), preferably -26 to -32C (-15 to -25F.); such composition having a melt viscosity of 3,000 to 30,000 cps. at 177C (350F), and being capable of setting up in less than 30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg.
(10 lb.), preferably at least 6.8 kg. (15 lb.)~ per page (18.7 to 19.1 cm. 7-3/8 to 7-1/2 in. long).
In addition to the adhesive described above, the present inven-tion also discloses a method for binding books containing a plurality of sheets by means of the perfect binding method, the steps for producing a spine for said books comprising;
(A) securing the edges of such sheets and applying thereto a molten film of hot melt non-pressure sensitive adhesive composition comprising on a weight basis, (1) 15-30% of at least one block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monorner;
(2) 5-10% of at least one ethylene vinyl acetate copolymer containing about 17 to 42% vinyl acetate; the weight ratio of the block polymer to the ethylene vinyl acetate copolymer being within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consiting of glycerol and pentaerythritol esters of natural and modified rosins;
(4) 25-35% of at least one WdX diluent which is solid at room temperature; and (5) 0.5 to 3% of at least one stabilizer;
said film being characterized by an Instron yield strength of 7.03 to 2S 14.06 kg./cm.2 (100 to 250 psi.) and a low temperature flexibility of less than -12C (10F); said composition having a melt viscosity of 3,000 to 30,000 cps. at 177C (350F), and a set up time of less than 3 ~
30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg. (10 lb.), preferably at least 6.8 kg.
(15 lb.), per page (18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long); and (B) allowing such film to solidify.
If a softcover book is to be formed, the cover is applied directly to the molten film, otherwise, the book is forwarded to be cased in using conventional techniques to form a hardcover book.
The block copolymer used herein may be more specifically described as an unvulcanized elastomeric block polymer wherein the respective monomeric moieties are arranged in an alternating sequence having the general configuration A-B-A wherein A is a nonelastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon monomer and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer, the total concentra-tion of the A block therein ranging from about 20 to 50%, based on the total weight of the polymer. An additional nomenclature which has been applied to these three unit block polymers is (SSSn-(BBB)n-(SSS)n wherein S represents the moieties derived from the vinyl 2n substituted aromatic hydrocarbon monomer in which the vinyl group is attached to a nuclear carbon atom and B represents the moieties derived from the conjugated diene monomer. Styrene is ordinarily used as the monovinyl aromatic hydrocarbon member, while butadiene-1,3 and isoprene are the most frequently used conjugated diene members. Thus, for example, sytrene-butadiene-styrene polymers are commercially available under the trade ~.~e6 "Kraton 11011' and "Kraton 1102", while styrene-isoprenestyrene polymers are commercial-7;~ '~
g "o~ rf~
ly available under the trade names "Kraton 1107" and "Kraton 1111."
All of the latter desisndted block polymers are sold by the Shell Chemical Company under the above trade ~ffles-.
Methods for preparing the latter block polymers are well known to those skilled in the art, typical procedures being disclosed in U.S. Pat. No. 3,265,765, issued Aug. 9, 1966. These procedures generally involve the solution polymerization of a mixture containing the monovinyl aromatic hydrocarbon monomer and the conjugated diene monomer in the presence of a catalyst of the formula R(Li)X Wherein x is an integer having the value of from 1 to 4 and R is a hydrocarbon radical selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals.
The ethylene-vinyl acetate copolymers useful herein are those copolymers containing from about 17 to about 42% vinyl acetate, pre-ferably 17 to 29%, based on the weight of the copolymer. Commercial-ly available ethylene-vinyl acetate copolymers that are especially ft~4~e,r,a,-~
suited for use herein are sold by DuPont under the ~r~ T~e- "Elvax".
For example, Elvax 250 contains 27.2 to 28,8% vinyl acecdte and has a melt index of 38-48 dg/min., while Elvax 420 contains 17.5 to 18.5%
vinyl acetate and has a melt index of 136-165 dg./min. The melt index is a value determined by ASTM D 1238 procedure and reflects the molten flow character of the copolymer. The higher the nurnber, the greater the flow, and vice versa. Greater flow also reflects lower molecular weight and lower molten viscosity, and vice versa. A blend of copolymers could be used by selectively choosing high and low melt index copolymers to arrive at a desired median melt index, viscosity etc.
While many tackifiers are known in the art for use in hot melt systems, we have found that superior performance is achieved herein by the use of rosin ester tackifiers. These tackifiers are selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins and include, for example, the glycerol ester of gum, tall or wood rosin, the glycerol ester of hydrogenated rosin and the pentaerythritol esters of the corresponding rosins.
The wax diluents employed herein are used to reduce the melt vis-cosity or cohesive characteristics of the hot melt adhesive composi-tions without appreciably decreasing their adhesive binding character-istics. Useful diluents are those which are solid at room tempera-ture and include the petroleum waxes, such as paraffin wax having a melting point of from about 130 to 165F. and microcrystalline waxes having a melting point of from about 140 to 200F. (the latter melt-ing points being determined by ASTM method D127-60), and synthetic waxes made by polymerizing carbon monoxide and hydrogen such as Fischer-Tropsch wax as well as the alpha-olefins containing at least 24 carbon atoms.
The stabilizers which are present in the hot melt systems herein serve to protect the otherwise vulnerable block polymer, and thereby the total adhesive system, from the thermal and oxidative degradation which is frequently encountered during the manufacture and application of the adhesive as well as in the ordinary exposure of the final ad-hered product. Such degradation is usually manifested by deteriora-tion in appearance, physical properties and performance. Among theapplicable stabilizers are included high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-t;t~ 73(~
contain,ng 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. In particular, tertiary butyl groups general-ly are substituted onto the benzene ring in at least one of the orthopositions relative to the phenolic hydroxy group. The presence of these sterically bulky substituted radicals in the vicinity of the hydroxyl group serves to retard its stretching frequency and, cor-respondingly, its reactivity, this steric hindrance thus providing the phenolic compound with its stabilizing properties.
Representative hindered phenols include the following:
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-hydroxyphenol)propionate;
n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4'-methylenebis (2,6-di-tert-butyl phenol); 2,2'-methylenebis (4-methyl-
said composition being characterized by an ability to form a film exhibiting Instron yield strenyths of 7.03-14.06 kg./cm.2 (100-250 psi.) and a low temperature flexibility of less than -12C (10F), preferably -26 to -32C (-15 to -25F.); such composition having a melt viscosity of 3,000 to 30,000 cps. at 177C (350F), and being capable of setting up in less than 30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg.
(10 lb.), preferably at least 6.8 kg. (15 lb.)~ per page (18.7 to 19.1 cm. 7-3/8 to 7-1/2 in. long).
In addition to the adhesive described above, the present inven-tion also discloses a method for binding books containing a plurality of sheets by means of the perfect binding method, the steps for producing a spine for said books comprising;
(A) securing the edges of such sheets and applying thereto a molten film of hot melt non-pressure sensitive adhesive composition comprising on a weight basis, (1) 15-30% of at least one block polymer having the general configuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monorner;
(2) 5-10% of at least one ethylene vinyl acetate copolymer containing about 17 to 42% vinyl acetate; the weight ratio of the block polymer to the ethylene vinyl acetate copolymer being within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consiting of glycerol and pentaerythritol esters of natural and modified rosins;
(4) 25-35% of at least one WdX diluent which is solid at room temperature; and (5) 0.5 to 3% of at least one stabilizer;
said film being characterized by an Instron yield strength of 7.03 to 2S 14.06 kg./cm.2 (100 to 250 psi.) and a low temperature flexibility of less than -12C (10F); said composition having a melt viscosity of 3,000 to 30,000 cps. at 177C (350F), and a set up time of less than 3 ~
30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg. (10 lb.), preferably at least 6.8 kg.
(15 lb.), per page (18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long); and (B) allowing such film to solidify.
If a softcover book is to be formed, the cover is applied directly to the molten film, otherwise, the book is forwarded to be cased in using conventional techniques to form a hardcover book.
The block copolymer used herein may be more specifically described as an unvulcanized elastomeric block polymer wherein the respective monomeric moieties are arranged in an alternating sequence having the general configuration A-B-A wherein A is a nonelastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon monomer and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer, the total concentra-tion of the A block therein ranging from about 20 to 50%, based on the total weight of the polymer. An additional nomenclature which has been applied to these three unit block polymers is (SSSn-(BBB)n-(SSS)n wherein S represents the moieties derived from the vinyl 2n substituted aromatic hydrocarbon monomer in which the vinyl group is attached to a nuclear carbon atom and B represents the moieties derived from the conjugated diene monomer. Styrene is ordinarily used as the monovinyl aromatic hydrocarbon member, while butadiene-1,3 and isoprene are the most frequently used conjugated diene members. Thus, for example, sytrene-butadiene-styrene polymers are commercially available under the trade ~.~e6 "Kraton 11011' and "Kraton 1102", while styrene-isoprenestyrene polymers are commercial-7;~ '~
g "o~ rf~
ly available under the trade names "Kraton 1107" and "Kraton 1111."
All of the latter desisndted block polymers are sold by the Shell Chemical Company under the above trade ~ffles-.
Methods for preparing the latter block polymers are well known to those skilled in the art, typical procedures being disclosed in U.S. Pat. No. 3,265,765, issued Aug. 9, 1966. These procedures generally involve the solution polymerization of a mixture containing the monovinyl aromatic hydrocarbon monomer and the conjugated diene monomer in the presence of a catalyst of the formula R(Li)X Wherein x is an integer having the value of from 1 to 4 and R is a hydrocarbon radical selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals.
The ethylene-vinyl acetate copolymers useful herein are those copolymers containing from about 17 to about 42% vinyl acetate, pre-ferably 17 to 29%, based on the weight of the copolymer. Commercial-ly available ethylene-vinyl acetate copolymers that are especially ft~4~e,r,a,-~
suited for use herein are sold by DuPont under the ~r~ T~e- "Elvax".
For example, Elvax 250 contains 27.2 to 28,8% vinyl acecdte and has a melt index of 38-48 dg/min., while Elvax 420 contains 17.5 to 18.5%
vinyl acetate and has a melt index of 136-165 dg./min. The melt index is a value determined by ASTM D 1238 procedure and reflects the molten flow character of the copolymer. The higher the nurnber, the greater the flow, and vice versa. Greater flow also reflects lower molecular weight and lower molten viscosity, and vice versa. A blend of copolymers could be used by selectively choosing high and low melt index copolymers to arrive at a desired median melt index, viscosity etc.
While many tackifiers are known in the art for use in hot melt systems, we have found that superior performance is achieved herein by the use of rosin ester tackifiers. These tackifiers are selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins and include, for example, the glycerol ester of gum, tall or wood rosin, the glycerol ester of hydrogenated rosin and the pentaerythritol esters of the corresponding rosins.
The wax diluents employed herein are used to reduce the melt vis-cosity or cohesive characteristics of the hot melt adhesive composi-tions without appreciably decreasing their adhesive binding character-istics. Useful diluents are those which are solid at room tempera-ture and include the petroleum waxes, such as paraffin wax having a melting point of from about 130 to 165F. and microcrystalline waxes having a melting point of from about 140 to 200F. (the latter melt-ing points being determined by ASTM method D127-60), and synthetic waxes made by polymerizing carbon monoxide and hydrogen such as Fischer-Tropsch wax as well as the alpha-olefins containing at least 24 carbon atoms.
The stabilizers which are present in the hot melt systems herein serve to protect the otherwise vulnerable block polymer, and thereby the total adhesive system, from the thermal and oxidative degradation which is frequently encountered during the manufacture and application of the adhesive as well as in the ordinary exposure of the final ad-hered product. Such degradation is usually manifested by deteriora-tion in appearance, physical properties and performance. Among theapplicable stabilizers are included high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-t;t~ 73(~
contain,ng 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. In particular, tertiary butyl groups general-ly are substituted onto the benzene ring in at least one of the orthopositions relative to the phenolic hydroxy group. The presence of these sterically bulky substituted radicals in the vicinity of the hydroxyl group serves to retard its stretching frequency and, cor-respondingly, its reactivity, this steric hindrance thus providing the phenolic compound with its stabilizing properties.
Representative hindered phenols include the following:
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-hydroxyphenol)propionate;
n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4'-methylenebis (2,6-di-tert-butyl phenol); 2,2'-methylenebis (4-methyl-
6-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,5-di-tertamyl hydroquinone; 2,6-di-tert-butyl phenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octylthio)-1,3,5-triazine; 2,4,6-tris-(4-hydroxy-3,5-di-tertbutylphenoxy)-1,3,5-triazine; tetrakis (methylene 3 3', 5-di-tert-buty4'-hydroxyphenyl propionate)-methane, di-n-octadecyl 3,5-di-tert-butyl4-hydroxybenzylphosphonate; 2-(n-octylthio)ethyl 3,5-di-tert-butyl-4hydroxybenzoate; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate].
The performance of these stabilizers may be further enhanced by utilizing, in conjunction therewith: (1) synergists such as, for example, thiodipropionate esters and phosphites; and (2) chelating agents and metal deactivators such as, for example, ethylenediamine r7~
tetraacetic aci d, salts thereof, and disalicylal propylenediimine.
With regard to proportions, the hot rnelt compositions of the present invention comprise on a weight basis 15-30%, preferably 18-25%, of the block copolymer; 5-10%, preferably 8-10~, of the ethylene 5 vinyl aceta-te copolymer; 25-40%, preferably 25-38%, of the tackifier, 25-35%, preferably 30-35%, of the wax and 0.2 to 3%, preferably 0.4-0.75%, of the stabilizer. In addition to meeting the percentage ranges described hereinabove, it is al so important to formulate the adhesives so as to assure that the weight ratio of block polymer to ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1.
Optional additives may be incorporated into the hot melt composi-tions herein in order to modify certain properties thereof. Among these additives may be included: colorants such as titanium dioxide;
fillers such as talc and clay; non-blocking agents, etc.
Not all compositions formulated within the component ranges described herein will inherently possess the requirements for the perfect binding of books and it may be necessary to adjust the various components and/or amounts within the claimed ranges or otherwise modify the formulation in order to obtain a suitable hot melt adhesive for particular stock, application~ etc. Thus, it may be necessary to change the melt index of the ethylene vinyl acetate co-polymer in order to obtain a composition having a melt viscosity with-in the requi red range. Lowering the vinyl acetate content with re-spect to the ethylene has been found to increase the yield strength.
Additionally, the yield strength rnay be increased by decreasing the amount of the block polymer. Higher level s of block polymer and/or lower levels of rosin ester will provide for better low temperature ~i 7~
flexibility. If it is desired to adjust the setting speed of the formulated adhesive, this may be done by selecting a tackifier having a higher softening point or by adding a higher melting point wax.
The adhesion page pull may be increased by adding more rosin ester.
It will be recognized that the above suggested modificatons serve only as guidelines and other methods familiar to those skilled in the art may be used to modify the basic adhesive formulations so as to achieve all the properties required of the hot melt adhesives herein.
The procedure for preparing these hot melt adhesive compositions 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 about 121-177C (250-350F), the precise temperature utilized depend-ing on the melting point of the particular tackifying resin. Whenthe resin has at least partially melted, mixing is initiated and the block polymer, ethylene vinyl acetate copolymer and stabilizer are added together with any optional additives whose presence may be de-sired. Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the remainder of the tackifying resin and the wax diluent are thoroughly and uniformly admixed therewith. The resulting hot melt adhesive composition is drawn off and may be used immediately in hot pots; or it may be molten-extruded into rope form or converted into pellets, rods, cylinders, slats or billets depend-ing on the equipment which is used to cool the hot melt down tosolidification, or it may be placed in cooling pans and held in bulk form for later use.
The hot melts herein are typically applied at temperatures rang-ing from about 149-204C (300-400F), a preferred melt viscosity of from about 3,000 to 30,000 centipoises, and a wet film thickness of from about 5 to 25 mils when utilized in the perfect binding operation of this invention. As previously noted, the basic perfect binding technique, as conceived by the novel process of this inven-tion, comprises the steps of : (1) printing, cutting, folding and arranging the signatures; (2) cutting the signatures to remove the signature folds and to expose a fully squared backbone; (3) roughing the backbone so as to expose the fibers at the back edge and make them more receptive to the hot melt composition; (4) applying the hot melt composition by rneans of any conventional equipment employed in the perfect binding industry so as to provide a continuous film or coating over the entire back surface of the sheets; (5) applying a suitable cover, for example, paper backing, kraft, crash or full cover, to the molten hot melt coating; (6) allowing the adhesive to solidify thereby forming the spine of the book; and (7) trimming the perfect bound book to the proper size. Subsequently, the edges of the front and ends of the sheet may be dyed or painted, when desired.
In a variation of the above described process, the application of the backing or cover to the molten hot melt coating in step (5) is omitted so that the molten adhesive on the spine is simply permitted to solidify. An additional coating (or coatings) of hot melt adhesive (either the same or other formulation) is subsequently applied on top of the first coating and, while the adhesive film is still in its molten form, a layer of crash and paper are bonded to the spine. The book as this stage is termed "lined-up" and may thereafter be "cased-3'~
in" by means of the secured crash and endsheets in conventional fashion so as to form a hardcover book. Other conventional methods for the formation of hardcover books may also be employed using the adhesive of the present invention.
In the examples which follow, all parts and percentages are given by weight unless otherwise noted.
Testing Procedures Viscosity is determined by a Brookfield Thermosel using a #27 spindle.
Low Temperature Flexibility - The molten hot melt was cast, by means of a heated Bird applicator, onto a polytetrafluroethylene-coated steel sheet yielding a film having a dry film thickness of 20 mils.
After cooling, the film specimen was stripped from the plate and cut into 1.27 x 5.08 cm. (1/2 x 2 in.) test specimens. A representative specimen was then placed in a temperature controlled, carbon dioxide cabinet for a period of 10 minutes whereupon it was immediately flexed to a 180 angle. Where the specimen did not crack as a result of this procedure, a second identical specimen was placed in the cabinet at a lower temperature and the flexing procedure repeated. The temperature at which the specimen eventually cracked was thus noted as its "low temperature flexibility" or "cold crack" value. As the latter value is decreased, there is a corresponding increase in the flexibility and stability which can be expected upon exposing these filrns and the books bound therewith to low temperature conditions. Instron Yield Strength This property was determined according to Test Method A of ASTM procedure D88256T utilizing an Instron Tensile Tester; the films having been prepared according to the method set forth in the above described "Iow Temperature Flexibility" test. Adhesion Page Pull -i 1 ;J ~3 ~ 3 r~
In this test a page is actually pulled out of a book by a clamping device that is connected to a force gauge. The best result is ob-tained when the page tears rather than pulls out of the book, how-ever, page pull values of 4.5 to 9.1 kg. (10 to 20 lb.) are accept-able.
EXAMPLE I
This example illustrates the preparation of a hot melt adhesive composition typical of the products herein as well as the improved properties thereof which enable it to be effectively utilized in a perfect binding operation.
A heavy duty mixer which had been heated to 149C (300F) and which was equipped with rotor blades was charged with 12.5 parts of a glycerol ester of rosin. This tackifying resin was partially melted.
Agitation was then initiated whereupon 20 parts Kraton 1101, 10 parts Elvax 260, and 0.4 parts tetrakis(methylene 3-3', 5-di-tert-butyl-4'-hydroxyphenyl propionate)methane as stabilizer were added slowly in order to prevent the formation of lumps. Heating and mixing were continued until a homogeneous mass was obtained whereupon 25.0 parts additional rosin ester and 32.5 parts wax were admixed therewith.
The resulting homogeneous hot melt composition had a melt vis-cosity of 6,125 cps. at 177C (350F), and produced films having a yield strength of 9.84 kg./cm.2 (140 psi.) and a cold crack value of -34 to -37C (-30 to -35F) The adhesive was used to bind a book including coated stock using the perfect binding techniques with no prior priming; it set up quickly (within 26 sec.), with no "stringing"
and produced a book exhibiting a page pull on coated stock of 6.2 kg.
(13.7 lb.).
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EXAMPLE II
This example illustrates the use of varying components and amounts in order to produce adhesives within the scope of the present invention.
Six adhesive compositions were prepared as in Example I using the component and amounts shown in Table I below. All compositions exhibited a set up time less than 26 seconds and were characteri zed by the viscosity, yield strength and cold crack characteristics also shown in Table I.
EXAMPLE III (comparative) The following compositions not suitable herein are presented for comparative purposes. They were prepared using the method described in Example I and were found unacceptable for use in a primerless perfect book binding applications including coated stock at least for the reasons noted.
Composition G - a typical ethylene vinyl acetate hot melt adhesive.
Elvax 260 30 parts Tackifying resin 35 parts Petroleum wax 35 parts Stabili zer 0.75 parts The composition exhibited a viscosity of 4,500, a too high yield strength of 42.18 kg./cm.2 (600 psi) and a too high cold crack of -1 to 1.7C (30 to 35F). When used to produce a "perfect bound" book, a page pull value of 6.4 kg. (14.2 lb.) was obtained, however, the book was very stiff and exhibited unacceptable "mousetrapping"
properties.
Compos tion H a product within the scope of U.S. Pat. 3,837,994 ~
(ci ted hereinabove).
3 ~
- 19 _ Kraton 1101 32.5 parts Glycerol ester of rosin 37.5 parts PetroleUIll WdX 30 parts Stabilizer 0.4 parts 5 This composition had a viscosity of 12,500 cps, a too low yield strength of 3.52 kg./cm.2 (50 psi.) and cold crack of -34 to -40C
(-30 tG -40F). When used without a primer in the perfect binding operation, it was slow to set thereby causing machining problems, and exhibited a page pull of only 3.8 kg. (8.3 lb.).
Composition I - a product within the range of the polymeric content described in the present invention but outside the blank polymer ethylene vinyl acetate copolymer ratio.
Kraton 1101 15 parts Elvax 260 10 parts Glycerol ester of rosin 40 parts Petroleum wax 35 parts Stabilizer 0.4 parts The composition had a viscosity of 2,250 cps, a yield strength of 15.47 kg./cm.2 (220 psi.) and cold crack of -6.~ to 3.9C (20 to 25F). Such a poor cold crack value rendered the product unacceptable for use in the perfect binding operation.
Composition J - a product outside the component ranges of the adhesives of the present invention herein.
Kraton 1101 31 parts Elvax 260 14 parts Pentaerythritol ester of rosin 50 parts Petroleum wax 12.5 parts Stabilizer 2.5 parts The composition had a viscosity of 27,000, a too high yield strength of 34.45 kg./cm.2 (49G psi.) and a relatively poor cold crack of -23 to -26C (-10 to -15F). Books prepared using this adhesive would be too stiff and exhibit unacceptable "mousetrapping" properties.
The performance of these stabilizers may be further enhanced by utilizing, in conjunction therewith: (1) synergists such as, for example, thiodipropionate esters and phosphites; and (2) chelating agents and metal deactivators such as, for example, ethylenediamine r7~
tetraacetic aci d, salts thereof, and disalicylal propylenediimine.
With regard to proportions, the hot rnelt compositions of the present invention comprise on a weight basis 15-30%, preferably 18-25%, of the block copolymer; 5-10%, preferably 8-10~, of the ethylene 5 vinyl aceta-te copolymer; 25-40%, preferably 25-38%, of the tackifier, 25-35%, preferably 30-35%, of the wax and 0.2 to 3%, preferably 0.4-0.75%, of the stabilizer. In addition to meeting the percentage ranges described hereinabove, it is al so important to formulate the adhesives so as to assure that the weight ratio of block polymer to ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1.
Optional additives may be incorporated into the hot melt composi-tions herein in order to modify certain properties thereof. Among these additives may be included: colorants such as titanium dioxide;
fillers such as talc and clay; non-blocking agents, etc.
Not all compositions formulated within the component ranges described herein will inherently possess the requirements for the perfect binding of books and it may be necessary to adjust the various components and/or amounts within the claimed ranges or otherwise modify the formulation in order to obtain a suitable hot melt adhesive for particular stock, application~ etc. Thus, it may be necessary to change the melt index of the ethylene vinyl acetate co-polymer in order to obtain a composition having a melt viscosity with-in the requi red range. Lowering the vinyl acetate content with re-spect to the ethylene has been found to increase the yield strength.
Additionally, the yield strength rnay be increased by decreasing the amount of the block polymer. Higher level s of block polymer and/or lower levels of rosin ester will provide for better low temperature ~i 7~
flexibility. If it is desired to adjust the setting speed of the formulated adhesive, this may be done by selecting a tackifier having a higher softening point or by adding a higher melting point wax.
The adhesion page pull may be increased by adding more rosin ester.
It will be recognized that the above suggested modificatons serve only as guidelines and other methods familiar to those skilled in the art may be used to modify the basic adhesive formulations so as to achieve all the properties required of the hot melt adhesives herein.
The procedure for preparing these hot melt adhesive compositions 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 about 121-177C (250-350F), the precise temperature utilized depend-ing on the melting point of the particular tackifying resin. Whenthe resin has at least partially melted, mixing is initiated and the block polymer, ethylene vinyl acetate copolymer and stabilizer are added together with any optional additives whose presence may be de-sired. Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the remainder of the tackifying resin and the wax diluent are thoroughly and uniformly admixed therewith. The resulting hot melt adhesive composition is drawn off and may be used immediately in hot pots; or it may be molten-extruded into rope form or converted into pellets, rods, cylinders, slats or billets depend-ing on the equipment which is used to cool the hot melt down tosolidification, or it may be placed in cooling pans and held in bulk form for later use.
The hot melts herein are typically applied at temperatures rang-ing from about 149-204C (300-400F), a preferred melt viscosity of from about 3,000 to 30,000 centipoises, and a wet film thickness of from about 5 to 25 mils when utilized in the perfect binding operation of this invention. As previously noted, the basic perfect binding technique, as conceived by the novel process of this inven-tion, comprises the steps of : (1) printing, cutting, folding and arranging the signatures; (2) cutting the signatures to remove the signature folds and to expose a fully squared backbone; (3) roughing the backbone so as to expose the fibers at the back edge and make them more receptive to the hot melt composition; (4) applying the hot melt composition by rneans of any conventional equipment employed in the perfect binding industry so as to provide a continuous film or coating over the entire back surface of the sheets; (5) applying a suitable cover, for example, paper backing, kraft, crash or full cover, to the molten hot melt coating; (6) allowing the adhesive to solidify thereby forming the spine of the book; and (7) trimming the perfect bound book to the proper size. Subsequently, the edges of the front and ends of the sheet may be dyed or painted, when desired.
In a variation of the above described process, the application of the backing or cover to the molten hot melt coating in step (5) is omitted so that the molten adhesive on the spine is simply permitted to solidify. An additional coating (or coatings) of hot melt adhesive (either the same or other formulation) is subsequently applied on top of the first coating and, while the adhesive film is still in its molten form, a layer of crash and paper are bonded to the spine. The book as this stage is termed "lined-up" and may thereafter be "cased-3'~
in" by means of the secured crash and endsheets in conventional fashion so as to form a hardcover book. Other conventional methods for the formation of hardcover books may also be employed using the adhesive of the present invention.
In the examples which follow, all parts and percentages are given by weight unless otherwise noted.
Testing Procedures Viscosity is determined by a Brookfield Thermosel using a #27 spindle.
Low Temperature Flexibility - The molten hot melt was cast, by means of a heated Bird applicator, onto a polytetrafluroethylene-coated steel sheet yielding a film having a dry film thickness of 20 mils.
After cooling, the film specimen was stripped from the plate and cut into 1.27 x 5.08 cm. (1/2 x 2 in.) test specimens. A representative specimen was then placed in a temperature controlled, carbon dioxide cabinet for a period of 10 minutes whereupon it was immediately flexed to a 180 angle. Where the specimen did not crack as a result of this procedure, a second identical specimen was placed in the cabinet at a lower temperature and the flexing procedure repeated. The temperature at which the specimen eventually cracked was thus noted as its "low temperature flexibility" or "cold crack" value. As the latter value is decreased, there is a corresponding increase in the flexibility and stability which can be expected upon exposing these filrns and the books bound therewith to low temperature conditions. Instron Yield Strength This property was determined according to Test Method A of ASTM procedure D88256T utilizing an Instron Tensile Tester; the films having been prepared according to the method set forth in the above described "Iow Temperature Flexibility" test. Adhesion Page Pull -i 1 ;J ~3 ~ 3 r~
In this test a page is actually pulled out of a book by a clamping device that is connected to a force gauge. The best result is ob-tained when the page tears rather than pulls out of the book, how-ever, page pull values of 4.5 to 9.1 kg. (10 to 20 lb.) are accept-able.
EXAMPLE I
This example illustrates the preparation of a hot melt adhesive composition typical of the products herein as well as the improved properties thereof which enable it to be effectively utilized in a perfect binding operation.
A heavy duty mixer which had been heated to 149C (300F) and which was equipped with rotor blades was charged with 12.5 parts of a glycerol ester of rosin. This tackifying resin was partially melted.
Agitation was then initiated whereupon 20 parts Kraton 1101, 10 parts Elvax 260, and 0.4 parts tetrakis(methylene 3-3', 5-di-tert-butyl-4'-hydroxyphenyl propionate)methane as stabilizer were added slowly in order to prevent the formation of lumps. Heating and mixing were continued until a homogeneous mass was obtained whereupon 25.0 parts additional rosin ester and 32.5 parts wax were admixed therewith.
The resulting homogeneous hot melt composition had a melt vis-cosity of 6,125 cps. at 177C (350F), and produced films having a yield strength of 9.84 kg./cm.2 (140 psi.) and a cold crack value of -34 to -37C (-30 to -35F) The adhesive was used to bind a book including coated stock using the perfect binding techniques with no prior priming; it set up quickly (within 26 sec.), with no "stringing"
and produced a book exhibiting a page pull on coated stock of 6.2 kg.
(13.7 lb.).
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EXAMPLE II
This example illustrates the use of varying components and amounts in order to produce adhesives within the scope of the present invention.
Six adhesive compositions were prepared as in Example I using the component and amounts shown in Table I below. All compositions exhibited a set up time less than 26 seconds and were characteri zed by the viscosity, yield strength and cold crack characteristics also shown in Table I.
EXAMPLE III (comparative) The following compositions not suitable herein are presented for comparative purposes. They were prepared using the method described in Example I and were found unacceptable for use in a primerless perfect book binding applications including coated stock at least for the reasons noted.
Composition G - a typical ethylene vinyl acetate hot melt adhesive.
Elvax 260 30 parts Tackifying resin 35 parts Petroleum wax 35 parts Stabili zer 0.75 parts The composition exhibited a viscosity of 4,500, a too high yield strength of 42.18 kg./cm.2 (600 psi) and a too high cold crack of -1 to 1.7C (30 to 35F). When used to produce a "perfect bound" book, a page pull value of 6.4 kg. (14.2 lb.) was obtained, however, the book was very stiff and exhibited unacceptable "mousetrapping"
properties.
Compos tion H a product within the scope of U.S. Pat. 3,837,994 ~
(ci ted hereinabove).
3 ~
- 19 _ Kraton 1101 32.5 parts Glycerol ester of rosin 37.5 parts PetroleUIll WdX 30 parts Stabilizer 0.4 parts 5 This composition had a viscosity of 12,500 cps, a too low yield strength of 3.52 kg./cm.2 (50 psi.) and cold crack of -34 to -40C
(-30 tG -40F). When used without a primer in the perfect binding operation, it was slow to set thereby causing machining problems, and exhibited a page pull of only 3.8 kg. (8.3 lb.).
Composition I - a product within the range of the polymeric content described in the present invention but outside the blank polymer ethylene vinyl acetate copolymer ratio.
Kraton 1101 15 parts Elvax 260 10 parts Glycerol ester of rosin 40 parts Petroleum wax 35 parts Stabilizer 0.4 parts The composition had a viscosity of 2,250 cps, a yield strength of 15.47 kg./cm.2 (220 psi.) and cold crack of -6.~ to 3.9C (20 to 25F). Such a poor cold crack value rendered the product unacceptable for use in the perfect binding operation.
Composition J - a product outside the component ranges of the adhesives of the present invention herein.
Kraton 1101 31 parts Elvax 260 14 parts Pentaerythritol ester of rosin 50 parts Petroleum wax 12.5 parts Stabilizer 2.5 parts The composition had a viscosity of 27,000, a too high yield strength of 34.45 kg./cm.2 (49G psi.) and a relatively poor cold crack of -23 to -26C (-10 to -15F). Books prepared using this adhesive would be too stiff and exhibit unacceptable "mousetrapping" properties.
Claims (7)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A non-pressure sensitive hot melt adhesive composition comprising on a weight basis:
(1) 15-30% of at least one block polymer having the general con-figuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
(2) 5-10% of at least one ethylene vinyl acetate copolymer containing 17 to 42% vinyl acetate, where the weight ratio of block polymer to ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins;
(4) 25-35% of at least one wax diluent which is solid at room temperature; and (5) 0.5% to 3% of at least one stabilizer;
said composition being characterized by an ability to form a film exhibiting Instron yield strengths of 100 to 250 psi. and a low temperature flexibility of less than -12°C (10°F), said composition having a melt viscosity of 3,000 to 30,000 cps. at 177°C (350°F) and being capable of setting up in less than 30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg.
(10 lb.) per page 18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long).
(1) 15-30% of at least one block polymer having the general con-figuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
(2) 5-10% of at least one ethylene vinyl acetate copolymer containing 17 to 42% vinyl acetate, where the weight ratio of block polymer to ethylene vinyl acetate copolymer is within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins;
(4) 25-35% of at least one wax diluent which is solid at room temperature; and (5) 0.5% to 3% of at least one stabilizer;
said composition being characterized by an ability to form a film exhibiting Instron yield strengths of 100 to 250 psi. and a low temperature flexibility of less than -12°C (10°F), said composition having a melt viscosity of 3,000 to 30,000 cps. at 177°C (350°F) and being capable of setting up in less than 30 seconds and, when applied to roughened signatures using perfect binding techniques, yielding a book having an adhesion page pull on coated stock of at least 4.5 kg.
(10 lb.) per page 18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long).
2. The composition of Claim 1, characterized in that the monovinyl aromatic hydrocarbon monomer moieties in the block polymer are derived from styrene and the conjugated diene monomer moieties are derived from butadiene-1,3 or isoprene.
3. The composition of Claim 1, characterized in that the ethylene vinyl acetate copolymer contains 17 to 29% vinyl acetate based on the weight of the copolymer.
4. The composition of Claim 1, characterized in that the tackifier is selected from the group consisting of the glycerol esters of gum, tall or wood rosin; the glycerol ester of hydrogenated rosin; and the pentaerythritol esters of the corresponding rosins.
5. A method for binding books containing a plurality of sheets by means of the perfect binding method, the steps for producing a spine for said books comprising:
(A) securing the edges of such sheets and applying thereto a molten film of a hot melt non-pressure sensitive adhesive composition comprising on a weight basis:
(1) 15-30% of at least one block polymer having the general con-figuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
(2) 5-10% of at least one ethylene vinyl acetate copolymer con-taining 17% to 42% vinyl acetate; the weight ratio of the block poly-mer to the ethylene vinyl acetate copolymer being within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins, (4) 25-35% of at least one wax diluent which is solid at room temperature; and (5) 0.5 to 3% of at least one stabilizer;
said film being characterized by an Instron yield strength of 7.03-14.06 kg./cm.2 (100 to 250 psi.) and a low temperature flexibility of less than -12°C (10°F), said composition having a melt viscosity of 3,000 to 30,000 cps. at 177°C (350°F) and a set up time of lessthan 30 seconds and, when applied to roughened signatures using perfect binding techniques yielding a book having an adhesion page pull on coated stock of at least 4.5 kg. (10 lb.) per page (18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long); and (B) allowing said film to solidify.
(A) securing the edges of such sheets and applying thereto a molten film of a hot melt non-pressure sensitive adhesive composition comprising on a weight basis:
(1) 15-30% of at least one block polymer having the general con-figuration A-B-A
wherein A is a non-elastomeric polymer block derived from the moieties of a monovinyl aromatic hydrocarbon radical and B is an elastomeric polymer block derived from the moieties of a conjugated diene monomer;
(2) 5-10% of at least one ethylene vinyl acetate copolymer con-taining 17% to 42% vinyl acetate; the weight ratio of the block poly-mer to the ethylene vinyl acetate copolymer being within the range of 1.75:1 to 6:1;
(3) 25-40% of at least one rosin ester tackifier selected from the group consisting of glycerol and pentaerythritol esters of natural and modified rosins, (4) 25-35% of at least one wax diluent which is solid at room temperature; and (5) 0.5 to 3% of at least one stabilizer;
said film being characterized by an Instron yield strength of 7.03-14.06 kg./cm.2 (100 to 250 psi.) and a low temperature flexibility of less than -12°C (10°F), said composition having a melt viscosity of 3,000 to 30,000 cps. at 177°C (350°F) and a set up time of lessthan 30 seconds and, when applied to roughened signatures using perfect binding techniques yielding a book having an adhesion page pull on coated stock of at least 4.5 kg. (10 lb.) per page (18.7 to 19.1 cm. - 7-3/8 to 7-1/2 in. long); and (B) allowing said film to solidify.
6. The process of Claim 5, further comprising the step of applying a cover to the film while the film is still in the molten state.
7. The process of Claim 5, wherein the book block is cased in to form a hardcover book.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/288,500 US4345349A (en) | 1981-07-30 | 1981-07-30 | Adhesive for perfect bound books and method of using same |
| US288,500 | 1981-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1178734A true CA1178734A (en) | 1984-11-27 |
Family
ID=23107383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000396605A Expired CA1178734A (en) | 1981-07-30 | 1982-02-19 | Adhesive for perfect bound books and method of using same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4345349A (en) |
| JP (1) | JPS604225B2 (en) |
| AU (1) | AU533459B2 (en) |
| CA (1) | CA1178734A (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8409015D0 (en) * | 1984-04-06 | 1984-05-16 | Eschem Ltd | Binding |
| DE3447702A1 (en) * | 1984-12-28 | 1986-07-10 | Planatolwerk Willy Hesselmann Chemische und Maschinenfabrik für Klebetechnik GmbH & Co KG, 8201 Rohrdorf | THERMOPLASTIC ADHESIVE ELEMENT AND METHOD FOR THE PRODUCTION AND USE THEREOF |
| US4772650A (en) * | 1985-04-12 | 1988-09-20 | Minnesota Mining And Manufacturing Co. | Polymeric coating for container induction innerseal |
| JPS627776A (en) * | 1985-07-05 | 1987-01-14 | Toagosei Chem Ind Co Ltd | Hot-melt adhesive composition |
| 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 |
| EP0279279A3 (en) * | 1987-02-18 | 1989-04-05 | National Starch and Chemical Corporation | Casing in hardcover books with hot melt adhesive composition |
| US4745140A (en) * | 1987-03-13 | 1988-05-17 | Chesebrough-Pond's Inc. | Aqueous adhesive composition containing N-vinyl lactam resin, tackifier, and ethylene/vinyl acetate emulsion stabilizer |
| IN171720B (en) * | 1987-08-31 | 1992-12-19 | Minnesota Mining & Mfg | |
| AU2917189A (en) * | 1987-12-31 | 1989-08-01 | Sakari John Malmberg | Synthetic paving or coating material |
| CA1335138C (en) * | 1988-05-04 | 1995-04-04 | Dennis D. Hansen | Hot-melt adhesive that has good open time at room temperature and can form creep-resistant bonds |
| US4942195A (en) * | 1988-08-17 | 1990-07-17 | National Starch And Chemical Investment Holding Corporation | Toughened rubber based hot melt adhesive compositions for bookbinding applications |
| US4944994A (en) * | 1988-08-17 | 1990-07-31 | National Starch And Investment Holding Corporation | Toughened hot melt adhesive composition for book casemaking |
| US5176779A (en) * | 1988-08-29 | 1993-01-05 | Minnesota Mining And Manufacturing Company | Fan-out padding using a hot melt adhesive |
| US5270068A (en) * | 1988-08-29 | 1993-12-14 | Minnesota Mining And Manufacturing Company | Edge-bonded sets of carbonless copy paper |
| US4907822A (en) * | 1988-09-26 | 1990-03-13 | National Starch And Chemical Corp. | Rounding of hard cover books |
| US4960295A (en) * | 1988-09-27 | 1990-10-02 | Eschem Inc. | Two-shot hot-melt bookbinding |
| US5151461A (en) * | 1989-02-07 | 1992-09-29 | Minnesota Mining And Manufacturing Company | Edge padding adhesive composition for carbonless papers |
| US5079068A (en) * | 1989-02-07 | 1992-01-07 | Minnesota Mining And Manufacturing Company | Adhesively edge-padding a stack of collated carbonless paper |
| CA2020705A1 (en) * | 1989-08-15 | 1991-02-16 | Stanley Decowski | Toughened base cup attachment adhesive |
| US5039726A (en) * | 1989-09-25 | 1991-08-13 | The Goodyear Tire & Rubber Company | Alkyl (C12-C22) esters of rosin acid |
| AU8627691A (en) * | 1990-09-13 | 1992-04-15 | Plan B, Inc. | Process and composition for protecting and cushioning exterior surfaces |
| EP0615433B1 (en) * | 1991-12-02 | 1997-03-12 | H.B. Fuller Licensing & Financing, Inc. | A thermoplastic adhesive composition and corresponding article |
| JPH06256740A (en) * | 1993-03-05 | 1994-09-13 | Nippon Synthetic Chem Ind Co Ltd:The | Water-soluble hot-melt adhesive |
| JP3499587B2 (en) * | 1993-10-05 | 2004-02-23 | 旭電化工業株式会社 | Hot melt adhesive with improved heat resistance |
| US5441999A (en) * | 1993-10-15 | 1995-08-15 | Reichhold Chemicals, Inc. | Hot melt adhesive |
| DE69508403T2 (en) * | 1994-07-26 | 1999-09-02 | Exxon Chemical Patents Inc | HOT MELT ADHESIVE BASED ON EVA AND STYROL BLOCK POLYMERS |
| EP0710737A3 (en) * | 1994-10-27 | 1998-01-07 | National Starch and Chemical Investment Holding Corporation | Hot melt adhesive compositions |
| US6034159A (en) * | 1995-01-06 | 2000-03-07 | H.B. Fuller Licensing & Financing, Inc. | Fast setting multipurpose bookbinding adhesive with excellent flexibility |
| US5836615A (en) * | 1995-05-10 | 1998-11-17 | Elliot, Deceased; Michael | Book construction with releasable adhesive |
| FR2739102B1 (en) * | 1995-09-26 | 1998-03-13 | Ceca Sa | SELF-ADHESIVE THERMOFUSIBLE ADHESIVE AND ITS USE FOR THE PREPARATION OF ADHESIVE TAPES |
| US5939483A (en) * | 1996-07-12 | 1999-08-17 | H.B. Fuller Licensing & Financing, Inc. | Low application temperature hot melt with excellent heat and cold resistance |
| WO2001046277A2 (en) | 1999-12-22 | 2001-06-28 | Exxonmobil Chemical Patents, Inc. | Polypropylene-based adhesive compositions |
| US6729784B2 (en) * | 2001-01-29 | 2004-05-04 | Ideas To Sales Llc | Securing shoelaces and other ties |
| JP2005099712A (en) * | 2003-08-28 | 2005-04-14 | Sharp Corp | Driving circuit of display device, and display device |
| US7148284B2 (en) * | 2004-05-21 | 2006-12-12 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesive |
| US20060229411A1 (en) * | 2005-04-06 | 2006-10-12 | Stephen Hatfield | Hot melt pressure sensitive adhesives based on blends of styrene/butadiene copolymers |
| US8283400B2 (en) * | 2008-06-09 | 2012-10-09 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
| US8431642B2 (en) * | 2008-06-09 | 2013-04-30 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
| US8242198B2 (en) * | 2008-06-09 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
| WO2010028523A1 (en) * | 2008-09-11 | 2010-03-18 | Lanxess Deutschland Gmbh | Hotmelt adhesives |
| US8431643B2 (en) * | 2009-05-29 | 2013-04-30 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and method of making thereof |
| US9109143B2 (en) | 2010-10-15 | 2015-08-18 | Exxonmobil Chemical Patents Inc. | Polypropylene-based adhesive compositions |
| MX341108B (en) * | 2012-05-24 | 2016-08-09 | Carvajal S A De C V * | Identifiable notebook with covered edges. |
| EP4069796A1 (en) * | 2019-12-04 | 2022-10-12 | ExxonMobil Technology and Engineering Company | Adhesive compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3837994A (en) * | 1968-04-25 | 1974-09-24 | T Flanagan | Manufacture of perfect bound books |
| US3686107A (en) * | 1968-06-25 | 1972-08-22 | Flintkote Co | Pressure-sensitive hot-melt adhesives |
| US3787531A (en) * | 1969-04-04 | 1974-01-22 | Minnesota Mining & Mfg | Pressure-sensitive adhesives comprising a block copolymer and a tackifier |
| US3644252A (en) * | 1969-05-13 | 1972-02-22 | Velsicol Chemical Corp | Adhesive compositions containing styrene/isobutylene copolymer |
| US3821143A (en) * | 1973-03-22 | 1974-06-28 | Du Pont | Hot melt adhesive composition containing a branched elastomeric copolymer |
| US3850858A (en) * | 1973-09-28 | 1974-11-26 | Eastman Kodak Co | Hot melt pressure sensitive adhesives |
| US4105611A (en) * | 1976-08-05 | 1978-08-08 | Norfin, Inc. | Adhesive composition and binding method |
| US4146521A (en) * | 1977-09-02 | 1979-03-27 | Eastman Kodak Company | Polyethylene containing hot melt adhesives |
-
1981
- 1981-07-30 US US06/288,500 patent/US4345349A/en not_active Expired - Lifetime
-
1982
- 1982-02-19 CA CA000396605A patent/CA1178734A/en not_active Expired
- 1982-03-03 AU AU81063/82A patent/AU533459B2/en not_active Expired
- 1982-05-06 JP JP57074694A patent/JPS604225B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU533459B2 (en) | 1983-11-24 |
| AU8106382A (en) | 1983-05-19 |
| US4345349A (en) | 1982-08-24 |
| JPS5827764A (en) | 1983-02-18 |
| JPS604225B2 (en) | 1985-02-02 |
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