CA1103833A - Poly(ester-amide) hot melt adhesive composition - Google Patents
Poly(ester-amide) hot melt adhesive compositionInfo
- Publication number
- CA1103833A CA1103833A CA270,799A CA270799A CA1103833A CA 1103833 A CA1103833 A CA 1103833A CA 270799 A CA270799 A CA 270799A CA 1103833 A CA1103833 A CA 1103833A
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- Canada
- Prior art keywords
- poly
- weight
- terephthalate
- ethylene
- parts
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Poly(ester-amide) adhesive compositions comprising a finely divided spheroidal metal. The poly(ester-amide) comprises crystalline polyester and amorphous polyamide segments formed by reaction of a C18 to C54 polycarboxylic acid mixture and a C2 to C10 aliphatic or alicyclic primary diamine. The finely divided spheroidal metal is selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc. The weight ratio of poly(ester-amide) to metal is in the range of 70:30 to 30:70. The adhesive compositions are useful as hot melt adhesives and cavity fillings.
Poly(ester-amide) adhesive compositions comprising a finely divided spheroidal metal. The poly(ester-amide) comprises crystalline polyester and amorphous polyamide segments formed by reaction of a C18 to C54 polycarboxylic acid mixture and a C2 to C10 aliphatic or alicyclic primary diamine. The finely divided spheroidal metal is selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc. The weight ratio of poly(ester-amide) to metal is in the range of 70:30 to 30:70. The adhesive compositions are useful as hot melt adhesives and cavity fillings.
Description
~3833 C-06-0~19 POLY(ESTER-A,\lIDE) HOT M~LT ~l)HESIVE ~OMPOSITI~N
__. _ _ BACKGROUND OF THr. INVENTION
The present inventioll relates to a poly(ester-amide) hot melt adheslve colnposition, to a method of filling voids with the adhesive composit:ion and to articles filled or coated wit1l the hot m~lt adhesive composition. Morè particularly, it refers to a block copoly~ester-amide) filled with a finely divided metal powder, to a method of filling voids with such a composition and to articles, filled or coate~ with the composition.
Hot melt adhesives are wèll known in the prior art.
These materials are conveniently a~plied to a substrate in the . molten state and upon cooling form an adhesive bond. However, a deiciency common to most o the hot melt adhesives of the prior art lS their tendency to soften and flQw at elevated temperatures, as, for examyle, 70 to 100C. with a resulting loss of bond strength. Consequently, these materials are not suitable for use over a broad temperature range.
Atte~pts to upgrade the softening and flow tempera-tures have involved using`very high molecular weight resinous materials and/or crosslinking of the resin. These methods have resulted in materials with higher softening points and flow temperatures. However, in most cases the resulting material was not adapted to thermal processing because of its higher molecular weight and/or crosslinked s~ructure resulting in extremely high application viscosity. Thus, ~hese ma~erials were not suitable for use as ho~ melt adhesives.
:' 06-12-0419 ~3~33 A definite need e~ists in the art for a hot melt adllcsive which is resistant to flow at temperatures around 150C. but which can be readily processed and applied using hot melt adhesive application techniques and apparatus.
U.S. Pcltent 3,650,999 discloses a poly(ester-amide) resill having improved adhesioll and high temperature peror-manco obtailled by reacting a crystalline polyester, a C18 to C54 polycarboxylic acid and a primary diamine. However, this poly~ester-amide) in common with other hot melt adhesives has deficiencies in creep resistance at temperatures above 150~C.
in the range up to 205C. and above and in shrinkage when the hot melt is cooled to room temperature after application.
A definite need therefore exists in the art for a hot melt adhesive which has improved creep resistance and lS shrink resistance without 1055 in processability and ease of application.
In the manufactuIe and repair of metal bodies such as automobiles and appliances, solder compositions containing -~
lead are frequently usçd to fill cavities and voids. These lead solders are a health hazard which mandates special hand-ling to protect workers and are also extremely dense. Conven-tional hot melt adhesives are not satisfactory for such cavity and void filling applications because they cannot be sanded rapidly at assembly line speed, they do not readily accept paint because they bleed through, and they do not withstand the curing temperatures for the paint. Curable adhesiues such as epoxies are generally unsatisfactory because they require careful metering of the components to provide good physical properties and bond strength, and because they take too long to cure to a sandable state.
A need therefore exists for a cavity or voi~l forming composition which is less dense and toxic than lead solder, forms a strong boncl to metal substrate, withstands extremes of humidity and temperature, is readily applied and rapiclly scts to a sandable state, is easily sanded smooth, and accepts paint witho~lt blecding through.
The needs are met by the adhesive composi.tions of the present invention wherein a poly(ester-amicle) having crystalline polyester segments and amorphous polya.mide segments is filled 1~ with a finely divided spheroidal metal powder.
The adhesive composit.ion comprises a) from about 70 to about 30 parts by weight of a ~-poly~ester-amide) block copolymer melting in the range of about 155C. to about 225C., having from about 30 to about 70 percent by . weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having :~ 2Q from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived rom an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an a~iphatlc .2S or alicyclic primary diamine containing 2 to 10 - . carbon atoms; and bj from about 30 to about 70 parts by weight of finely divided spheroi.dal metal powder selected from the . group consisting of aluminum, iron, mild steel, : 3a stainless stcel and zinc.
:;
~': ' . - ~ ' ~ 3~ 3 ~
Another aspect of the in~ention is directed to substrates coated with the adhesive composition and yet another aspect is directed to a method of filling a cavity in a sub-strate which comprises app]ying the adllesive composition as a hot melt to fill the cavity~ cooling the adhesive compos;tion below its crystalli~ation temperature and sanding the adhesive compositioll to providq a surface even with the surrounding substrate.
The poly(ester-amide) component of the present inven-tion i5 prepared by reacting a crystalline polyester with an _ amorphous polyamide or with the component polycarboxylic acid - and diamine by the one step or two step method set forth in U.S. 3,650,999 which patent is incor~orated herein by reference.
The polyester reactant is considered to be a prepoly-mer in view of the fact that it copolymerizes with the other reactants to form a block copolymer. The polyester must be capable of contributing a crystalline structure to the resul't-ing polytester-amide) as ls evidenced by a crystalline melting poin* as determined ~y diferential thermal analysis (DTA) and~or differential scanning calorimetry (DSC) methods. Moreover, the polyester should have a melting poînt higher than 180C. and preferably in the range of from 200 to 270C. and an inherent ~iscosity in the range of rom 0.05 to 0.70 when measured as a 0.5 gram solution of polyester in 100 ml. of a 60/40 phenol/
tetrachloroethane solvent pair at 25C.
The present invention uses a polyester reactant that contributes crystalline blocks to the resulting poly~ester-amide) hot melt adhesive composition. Consequently, optimum bulk stage physical properties such as tensile and high modulus are achieved without occurring the disadvanta~e of a high processing viscosity.
An inherent viscosity of ~rom 0.05 ~o 0.70 is required for the polyester i.n order to insure that the polyester will con-tribute the optimum crystalline strllcture to ~.he final polymeric product. Polyesters wi.th an intrinsic viscosity below 0.05 have a short chain length and cannot contribute the necessary crystalline structurc to th~ final polymeric product which also comprises amorphous polyamidc blocks Inherent viscosities greater tha.n about 0.70 re~llire exccssive reaction times or tem-peratures to form homogenous poly(ester-amides). Thus, it is impractical to use polyester reacta.nts with intrinsic ~iscosities greater than 0.70 in the practice of the present invention.
Moreo~er, excessive reaction times and temperatures tend to cause degradation of the polymer and a subsequent loss in adhesive properties.
1~ The minimum melting point requirement of about 180C.
for the polyester reactant is necessary in order to insure thatthe final polymeric product has excellent thermal properties .:
such as resistance to flow at elevated temperatures. Preferably, the melting point of the polyester is in the range of rom 200C.
to 270C .
Representatire .examples of high melting crystalline polyesters suitable or use in the present invention include polymeric ethylene terephthalate, neopentyl terephthalate, ethylene 2,6-naphthalate, tetramethylene terephthalate, tetra-methylene 2,6-naphthalate, trimethylene:2,6-naphthalate, 1,4-cyclohexylene dimethylene terephthalate, and copolyesters, such as copolyesters of ethylene terephthalate containing at least 50 mol percent of ethylene terephthalate, such as 95/59 90/10, 85/15 and 50/50 ethylene terepllthalate-ethylene ~ ~ 3~ ~ 3 isophthalate copolyesters, ethylene~tercphthalate-ethylene adi-pate copolyesters, and cthylcne terephthalate-ethylene hexahydro-terepllthalate copolyesters, tetrametllylene terepllthalate-tetra-methylene azelate copolyesters contclining at lcast 80 mol percent S of tetramethylene t:erephthalate, 1,4-cyclohexylene dimethylcne terephtllalate-~zelate copolyesters containin~ 70 to 90 mol per-cent of l,~-cyclohexylene dimethylene terephthalate, copolyesters of ethylene 2,5- and 2,6-naphthalate containing from 80 to 90 mol percent o-f the ethylene naphthalate, such as ethy]ene 2,5-naphthalate-ethylene azelate and ethylene 2,6-naphthalate-ethylene azelate copolyesters. These polyester blocks can be derived from various dicarboxylic acids and various glycols.
Representative examples of such acids are terephthalic acid, isophthalic acid, hexahydroterephthalic acid9 the naphthalic acids, such as 2,6-, 2,7-, 2,~-, 1,5- and l,4-nap]lthalene dicar-boxylic acids and other such acids which form high melting polyester resins. Examples of glycols are ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol and other such ~`
glycols. High melting polymers containing components such as
__. _ _ BACKGROUND OF THr. INVENTION
The present inventioll relates to a poly(ester-amide) hot melt adheslve colnposition, to a method of filling voids with the adhesive composit:ion and to articles filled or coated wit1l the hot m~lt adhesive composition. Morè particularly, it refers to a block copoly~ester-amide) filled with a finely divided metal powder, to a method of filling voids with such a composition and to articles, filled or coate~ with the composition.
Hot melt adhesives are wèll known in the prior art.
These materials are conveniently a~plied to a substrate in the . molten state and upon cooling form an adhesive bond. However, a deiciency common to most o the hot melt adhesives of the prior art lS their tendency to soften and flQw at elevated temperatures, as, for examyle, 70 to 100C. with a resulting loss of bond strength. Consequently, these materials are not suitable for use over a broad temperature range.
Atte~pts to upgrade the softening and flow tempera-tures have involved using`very high molecular weight resinous materials and/or crosslinking of the resin. These methods have resulted in materials with higher softening points and flow temperatures. However, in most cases the resulting material was not adapted to thermal processing because of its higher molecular weight and/or crosslinked s~ructure resulting in extremely high application viscosity. Thus, ~hese ma~erials were not suitable for use as ho~ melt adhesives.
:' 06-12-0419 ~3~33 A definite need e~ists in the art for a hot melt adllcsive which is resistant to flow at temperatures around 150C. but which can be readily processed and applied using hot melt adhesive application techniques and apparatus.
U.S. Pcltent 3,650,999 discloses a poly(ester-amide) resill having improved adhesioll and high temperature peror-manco obtailled by reacting a crystalline polyester, a C18 to C54 polycarboxylic acid and a primary diamine. However, this poly~ester-amide) in common with other hot melt adhesives has deficiencies in creep resistance at temperatures above 150~C.
in the range up to 205C. and above and in shrinkage when the hot melt is cooled to room temperature after application.
A definite need therefore exists in the art for a hot melt adhesive which has improved creep resistance and lS shrink resistance without 1055 in processability and ease of application.
In the manufactuIe and repair of metal bodies such as automobiles and appliances, solder compositions containing -~
lead are frequently usçd to fill cavities and voids. These lead solders are a health hazard which mandates special hand-ling to protect workers and are also extremely dense. Conven-tional hot melt adhesives are not satisfactory for such cavity and void filling applications because they cannot be sanded rapidly at assembly line speed, they do not readily accept paint because they bleed through, and they do not withstand the curing temperatures for the paint. Curable adhesiues such as epoxies are generally unsatisfactory because they require careful metering of the components to provide good physical properties and bond strength, and because they take too long to cure to a sandable state.
A need therefore exists for a cavity or voi~l forming composition which is less dense and toxic than lead solder, forms a strong boncl to metal substrate, withstands extremes of humidity and temperature, is readily applied and rapiclly scts to a sandable state, is easily sanded smooth, and accepts paint witho~lt blecding through.
The needs are met by the adhesive composi.tions of the present invention wherein a poly(ester-amicle) having crystalline polyester segments and amorphous polya.mide segments is filled 1~ with a finely divided spheroidal metal powder.
The adhesive composit.ion comprises a) from about 70 to about 30 parts by weight of a ~-poly~ester-amide) block copolymer melting in the range of about 155C. to about 225C., having from about 30 to about 70 percent by . weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having :~ 2Q from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived rom an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an a~iphatlc .2S or alicyclic primary diamine containing 2 to 10 - . carbon atoms; and bj from about 30 to about 70 parts by weight of finely divided spheroi.dal metal powder selected from the . group consisting of aluminum, iron, mild steel, : 3a stainless stcel and zinc.
:;
~': ' . - ~ ' ~ 3~ 3 ~
Another aspect of the in~ention is directed to substrates coated with the adhesive composition and yet another aspect is directed to a method of filling a cavity in a sub-strate which comprises app]ying the adllesive composition as a hot melt to fill the cavity~ cooling the adhesive compos;tion below its crystalli~ation temperature and sanding the adhesive compositioll to providq a surface even with the surrounding substrate.
The poly(ester-amide) component of the present inven-tion i5 prepared by reacting a crystalline polyester with an _ amorphous polyamide or with the component polycarboxylic acid - and diamine by the one step or two step method set forth in U.S. 3,650,999 which patent is incor~orated herein by reference.
The polyester reactant is considered to be a prepoly-mer in view of the fact that it copolymerizes with the other reactants to form a block copolymer. The polyester must be capable of contributing a crystalline structure to the resul't-ing polytester-amide) as ls evidenced by a crystalline melting poin* as determined ~y diferential thermal analysis (DTA) and~or differential scanning calorimetry (DSC) methods. Moreover, the polyester should have a melting poînt higher than 180C. and preferably in the range of from 200 to 270C. and an inherent ~iscosity in the range of rom 0.05 to 0.70 when measured as a 0.5 gram solution of polyester in 100 ml. of a 60/40 phenol/
tetrachloroethane solvent pair at 25C.
The present invention uses a polyester reactant that contributes crystalline blocks to the resulting poly~ester-amide) hot melt adhesive composition. Consequently, optimum bulk stage physical properties such as tensile and high modulus are achieved without occurring the disadvanta~e of a high processing viscosity.
An inherent viscosity of ~rom 0.05 ~o 0.70 is required for the polyester i.n order to insure that the polyester will con-tribute the optimum crystalline strllcture to ~.he final polymeric product. Polyesters wi.th an intrinsic viscosity below 0.05 have a short chain length and cannot contribute the necessary crystalline structurc to th~ final polymeric product which also comprises amorphous polyamidc blocks Inherent viscosities greater tha.n about 0.70 re~llire exccssive reaction times or tem-peratures to form homogenous poly(ester-amides). Thus, it is impractical to use polyester reacta.nts with intrinsic ~iscosities greater than 0.70 in the practice of the present invention.
Moreo~er, excessive reaction times and temperatures tend to cause degradation of the polymer and a subsequent loss in adhesive properties.
1~ The minimum melting point requirement of about 180C.
for the polyester reactant is necessary in order to insure thatthe final polymeric product has excellent thermal properties .:
such as resistance to flow at elevated temperatures. Preferably, the melting point of the polyester is in the range of rom 200C.
to 270C .
Representatire .examples of high melting crystalline polyesters suitable or use in the present invention include polymeric ethylene terephthalate, neopentyl terephthalate, ethylene 2,6-naphthalate, tetramethylene terephthalate, tetra-methylene 2,6-naphthalate, trimethylene:2,6-naphthalate, 1,4-cyclohexylene dimethylene terephthalate, and copolyesters, such as copolyesters of ethylene terephthalate containing at least 50 mol percent of ethylene terephthalate, such as 95/59 90/10, 85/15 and 50/50 ethylene terepllthalate-ethylene ~ ~ 3~ ~ 3 isophthalate copolyesters, ethylene~tercphthalate-ethylene adi-pate copolyesters, and cthylcne terephthalate-ethylene hexahydro-terepllthalate copolyesters, tetrametllylene terepllthalate-tetra-methylene azelate copolyesters contclining at lcast 80 mol percent S of tetramethylene t:erephthalate, 1,4-cyclohexylene dimethylcne terephtllalate-~zelate copolyesters containin~ 70 to 90 mol per-cent of l,~-cyclohexylene dimethylene terephthalate, copolyesters of ethylene 2,5- and 2,6-naphthalate containing from 80 to 90 mol percent o-f the ethylene naphthalate, such as ethy]ene 2,5-naphthalate-ethylene azelate and ethylene 2,6-naphthalate-ethylene azelate copolyesters. These polyester blocks can be derived from various dicarboxylic acids and various glycols.
Representative examples of such acids are terephthalic acid, isophthalic acid, hexahydroterephthalic acid9 the naphthalic acids, such as 2,6-, 2,7-, 2,~-, 1,5- and l,4-nap]lthalene dicar-boxylic acids and other such acids which form high melting polyester resins. Examples of glycols are ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol and other such ~`
glycols. High melting polymers containing components such as
2,2-dimethyl propane diol, form polyesters which have melting - points above 234C. Mixtures of the oregoing polyesters can also be used.
Prçerably, a polyester from the following group is used to prepare the polyesteramide component of the present invention:
Poly(ethylene terephthalate/isophthalate), 100/0 to 75/25;
Poly(ethyelnelhexamethylene terephthalate), lO0/0 to 75/25;
Poly(ethylene/neopentyl terephthalate), 100/0 to 75/25;
Pol~(tetramethylene terephthalate~isophthalate), 100~0 to 75/25;
Poly(tetramethylene/hexamethylene terephthalate), 100/0 to 75~25;
Poly(tetramethylene~neopentyl terephthalate), 100/0 to 75/25;
Poly(ethylene/propyle}le terephthalate), 100~0 to 60/~0; and Poly(tetramethylene - 2,6 - naphthalate~terephthalate), 100/0 to 75/25; etc.
The amide portion of the polyester-amide adhesive com-ponents of thls invention are amorphous block segments which contribute wettability, elasticity and rubber character to the adhesive composition. The polyamide portion of the polyester-amide composition of the present invention is the reaction pro-duct of a C18 to C54 polycarboxylic acid and an aliphatic primary diamine. The polycarboxylic acids are well known in the art and are describad in detail in U. S. Patent 3,157,681.
These materials are available commerciall~as mixtures of mono-~0 basic, dibasic and tribasic acid with the dibasic acid beingpresent as the major component of the mixtures. These materials generally have a composition as follows:
Percent by Weight C18 monobasic acids 0 - 10 (Monoacids) C36 dibasic acids 80 - 100 (Dimer acids) C54 and higher polybasic acids 0 - 10 (Trimer acids~
.
~, ~ ~ 3~ 3 ~
The relati~e ratios of monomer, dimcr and trimer in such unfractionatcd ~olymcric fat acids are dependent on the nature of the startillg materials and thc conditions of poly-merization. ~or the purposcs o this lnventlon, the term poly-c~rboxylic also includes mlxtures of the mono, di and tribasicacids.
The aliphatic or alicyclic primary diamines used in this invention oontain from 2 to 10 carbon atoms. These include ethylene diamine, 1~3-propane diamine, 1,4-butanediamine, 1,5-pentane diamine, hexamethylene diamine, l,10-decanediamine2 cyclohexyldiamine, 2,2-dimethyl-1,3-propane diamine, etc.
Optionally up to 60 percent by weight of a linear ali-phatic dibasic acid having from 4 to 10 carbon atoms may be substituted for a corresponding amount of the C18 to C54 poly-carboxylic acid used to prepare this portion of the polyester- --amide. Examples oE these acids would include oxalic, malonic, succinic; glutaric, adipic, pimelic, suberic, azelaic, and sebacic acids. The advantage of substituting the C4 to C10 acids for the C18 to C54 acids is to permit more heterogenous character to the polyamide portion o-f the polymer in those applications where a more heterogenous character is desired.
The poly(ester-amide) component of the present inven-tion contains 30 to 70 percent by weight of polyamide segment and correspondingly, from 30 to 70 percent by weight of crystalline polyester segments. Preferably, it contains 40 to 60 percent by weight of polyamide segment and correspondingly, from 60 to 40 percent of crystalline polyester segments. The poly(ester-amides) are further characterized as having an inherent viscosity in the range of from 0.35 to 0.95 an~ more preferably from ~ 3~ 3 ~
0.40 to 0.6 when measllred as a 0.5 gram solution of poly(ester-amide) in 100 ml. of a 60/40 phenol/~etrachloroethane solvent pair at 25~C. The crystalline melting point of these materials as measured by DTA or DSC is in the range of from 155C. to 225C.
and the melt v:iscosity at 220C, is in the range of fro~n 5000 to 65,000 centipo.ises. The poly(ester-amide) resins are soluble in a 60~40 phenol/tctrachloro~thane solvent pair and insoluble in a 1/1 toluene/isopropanol solvent pair. Moreover, the 1/1 toluene/
isopropanol extractable content of the poly(ester-amide) resins is less than 2 percent. In view of the fact that the polyamide portion is soluble in toluene/isopropanol solvent pair the very low order of extractables for the poly(ester-amide) resins demon-strates that they are true block copolymers and not physical blends of polyester and polyamid0 segments.
lS The polytester-amide) is prepared by a one step or two step method. In the one step method the acid and amine components, which go to form the polyamide segment are polymerized in the presence of the crystalline polyester prepolymer. In the two step method the polyamide and polyester prepolymer segments are pre-pared separately and ~hen 'reacted together ~o form the polyester-amide. These methods are,discussed in greater detail in the working examples o~ U.S. Patent 3,650,999.
The morphological proper~ies of the poly~ester-amides) are determined on a duPont differential thermal analyzer Model DTA 900 using the differential scanning calorimeter attachment, with a 5 to 25 mg sample heated at a rate of 20C. in a nitrogen atmosphere. The glass transition point (Tg) is the onset of the increase in specific heat of the polymer and is the intersection ~' of the base line and the slope of increasing specific hcat; the' melting point (Tm) is the temperature observed at the apex of the melting endother~ peak.
, 9 ' .
Prçerably, a polyester from the following group is used to prepare the polyesteramide component of the present invention:
Poly(ethylene terephthalate/isophthalate), 100/0 to 75/25;
Poly(ethyelnelhexamethylene terephthalate), lO0/0 to 75/25;
Poly(ethylene/neopentyl terephthalate), 100/0 to 75/25;
Pol~(tetramethylene terephthalate~isophthalate), 100~0 to 75/25;
Poly(tetramethylene/hexamethylene terephthalate), 100/0 to 75~25;
Poly(tetramethylene~neopentyl terephthalate), 100/0 to 75/25;
Poly(ethylene/propyle}le terephthalate), 100~0 to 60/~0; and Poly(tetramethylene - 2,6 - naphthalate~terephthalate), 100/0 to 75/25; etc.
The amide portion of the polyester-amide adhesive com-ponents of thls invention are amorphous block segments which contribute wettability, elasticity and rubber character to the adhesive composition. The polyamide portion of the polyester-amide composition of the present invention is the reaction pro-duct of a C18 to C54 polycarboxylic acid and an aliphatic primary diamine. The polycarboxylic acids are well known in the art and are describad in detail in U. S. Patent 3,157,681.
These materials are available commerciall~as mixtures of mono-~0 basic, dibasic and tribasic acid with the dibasic acid beingpresent as the major component of the mixtures. These materials generally have a composition as follows:
Percent by Weight C18 monobasic acids 0 - 10 (Monoacids) C36 dibasic acids 80 - 100 (Dimer acids) C54 and higher polybasic acids 0 - 10 (Trimer acids~
.
~, ~ ~ 3~ 3 ~
The relati~e ratios of monomer, dimcr and trimer in such unfractionatcd ~olymcric fat acids are dependent on the nature of the startillg materials and thc conditions of poly-merization. ~or the purposcs o this lnventlon, the term poly-c~rboxylic also includes mlxtures of the mono, di and tribasicacids.
The aliphatic or alicyclic primary diamines used in this invention oontain from 2 to 10 carbon atoms. These include ethylene diamine, 1~3-propane diamine, 1,4-butanediamine, 1,5-pentane diamine, hexamethylene diamine, l,10-decanediamine2 cyclohexyldiamine, 2,2-dimethyl-1,3-propane diamine, etc.
Optionally up to 60 percent by weight of a linear ali-phatic dibasic acid having from 4 to 10 carbon atoms may be substituted for a corresponding amount of the C18 to C54 poly-carboxylic acid used to prepare this portion of the polyester- --amide. Examples oE these acids would include oxalic, malonic, succinic; glutaric, adipic, pimelic, suberic, azelaic, and sebacic acids. The advantage of substituting the C4 to C10 acids for the C18 to C54 acids is to permit more heterogenous character to the polyamide portion o-f the polymer in those applications where a more heterogenous character is desired.
The poly(ester-amide) component of the present inven-tion contains 30 to 70 percent by weight of polyamide segment and correspondingly, from 30 to 70 percent by weight of crystalline polyester segments. Preferably, it contains 40 to 60 percent by weight of polyamide segment and correspondingly, from 60 to 40 percent of crystalline polyester segments. The poly(ester-amides) are further characterized as having an inherent viscosity in the range of from 0.35 to 0.95 an~ more preferably from ~ 3~ 3 ~
0.40 to 0.6 when measllred as a 0.5 gram solution of poly(ester-amide) in 100 ml. of a 60/40 phenol/~etrachloroethane solvent pair at 25~C. The crystalline melting point of these materials as measured by DTA or DSC is in the range of from 155C. to 225C.
and the melt v:iscosity at 220C, is in the range of fro~n 5000 to 65,000 centipo.ises. The poly(ester-amide) resins are soluble in a 60~40 phenol/tctrachloro~thane solvent pair and insoluble in a 1/1 toluene/isopropanol solvent pair. Moreover, the 1/1 toluene/
isopropanol extractable content of the poly(ester-amide) resins is less than 2 percent. In view of the fact that the polyamide portion is soluble in toluene/isopropanol solvent pair the very low order of extractables for the poly(ester-amide) resins demon-strates that they are true block copolymers and not physical blends of polyester and polyamid0 segments.
lS The polytester-amide) is prepared by a one step or two step method. In the one step method the acid and amine components, which go to form the polyamide segment are polymerized in the presence of the crystalline polyester prepolymer. In the two step method the polyamide and polyester prepolymer segments are pre-pared separately and ~hen 'reacted together ~o form the polyester-amide. These methods are,discussed in greater detail in the working examples o~ U.S. Patent 3,650,999.
The morphological proper~ies of the poly~ester-amides) are determined on a duPont differential thermal analyzer Model DTA 900 using the differential scanning calorimeter attachment, with a 5 to 25 mg sample heated at a rate of 20C. in a nitrogen atmosphere. The glass transition point (Tg) is the onset of the increase in specific heat of the polymer and is the intersection ~' of the base line and the slope of increasing specific hcat; the' melting point (Tm) is the temperature observed at the apex of the melting endother~ peak.
, 9 ' .
3~
The s~cond co~nponent of the adhesive composition is a finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc. The metal powdcr is substantially uniformly dispersecl in the poly(~ster-amid0). It m~y be of number average particle size in the range of 0.2 micron to 150 micron and is preferably of number average particlc size ;n the range of 4 to 100 micron.
The preferred metal filler is atomized aluminum particularly when the adhesive composition is used for cavity filling since it allows the hot melt composition to be readily smoothed and burnished when it is sanded. In general,plate-like, acicular, or multi-faceted granular powdered metals are unsatisfactory, surprisingly causing high viscosity in the hot melt and "blinding"
or filling and occlusion of sand paper when the filled composition is sanded.
The amount of metal po~der which is dispersed in the poly(ester-amide) is sufficient to improve the high temperature creep resistance without causing unmanageable rheology. It is preferably in the range of about 30 to about 7U parts by weight of metal powder dispersed in about 70 to about 30 parts by weight of poly(ester-amide). The melt viscosity of the hot melt composition containing the metal iller is preferably less than about 150,000 centipoises at a temperature of 232C. and a shear rate of 3-4 sec. measured in a Brookfield Thermocel Unit Model HBT. Above 150,000 centipoise melt viscosity, the hot melt is difficult to apply and spread, and tends to be dragged from the point of application.
Creep resistance of the filled poly(ester-amide) com-positions of the present invention is determined by observing .
.
~3~333 the sag of a 10 to 15 ~ram sample of the compositi~n placed on an alulninum plane inclined at 60 to the vertical. Thc obser-vations are carried out at 175 and 205C. Creep or sag in less than 60 minutes at the designated temperature is recorded as a failure to meet the test.
Lap bond l:ens;le strengt}l is de~.ermined by AST~I Test Metllod D-1002-72. A mil~imulll of 100 kg per sq. cm. is preferred.
Sandability of the filled compositions is determined by applying the compasition as a hot melt to a smooth steel panel 7.5 cm. x 22.5 cm. to provide a strip 4 cm. wide and in the range of 25 to 250 microns thick. The panel is cooled to room tempera-ture and a disc sander, 12.5 cm. diameter, with 80 grit medium tungsten carbide abrasive, is applied to the composition at 1000 rpm to smooth and feather the composition. I the surface of the composition becomes smooth enough to accept paint without '-'telegraphing"or showing a difference in refIectivity between the painted steel and the painted composition, and without blinding or blocking the abrasive surface of the sander, the composition , is rated sandable.
When the hot melt composition is formed by mixing the filler with the melted polymer, a good mix is considered to have been obtained if the filler particles are evenly distribu~ed throughout the melt. In poor mlxes, the filler particles are , not adequately wet by the melt, and are not evenly distributed Z5 remaining aggregated within the melt. Melt stability of the mix is determined by maintaining the mix at 216C. for two hours.
If ths melt viscosity changes less than ~10 percent during this time, the mix is considered to have melt stability.
:`
.
- - ~
~ 3 3 Tn addition to improving t~le creep resis~ance of the poly(~ster-amide) component, the metallic component improves the rate of melting of tlle adhcsive composition, allows the composition to be applicd and spread molc easily wit~l less pressure, imp~rts longer "opell" timc bct~een application of the hot melt and closing o~ tlle bond and higher "green" strength or aster onset of bond strength, and reduces the degree of shrinkage of the adhesive composition when lt is cooled from the hot melt te~perature to ambient temperature. The cost of the composition is also considerably reduced. When the composi-tion is used to fill cavities, it can be readily sanded as dis-cussed above, withstands extremes of temperature and humidity, is exceptionally solvent resistant and is readily painted without absorbing solven~, swelling, and blistering.
The hot melt adhesive compositions of the present invention find widespread utility where~er hot melt adhesives are used. They are especially valuable in those applications where resistance to creep at elevated temperatures is a necessary requirement. The adhesive compositions of the present invention may be used to great advantage to bond a variety of substrates including metal, glass, synthetic and natural textiles, leathers, synthetic polymeric sheet material, wood, paper, etc.
The present invention also includes the concept of incorporating various ingredients into the poly~ester-amide) resins of the present invention in order to improve processing and/or performance of these materials. These additives and adjuncts include antioxidants 9 thermal stabilizers~ extenders, dyes, pigments, adhesion promoters, plasticizers, etc.
.
~ ~ 3~ 3 ~
The following examples are sct for~h in illustration of this invention and should not be construed as a limitation thereof. Unless otllerwise ind;cated, all parts and percentages are by weight.
EXAM_L~ I
A block copolymel which is appro~imately 60 percen~
by weight crystalline polyethylene terepht}lalate segments and 40 percent by weight amorphous polyamide made from dimcr acid and hexamethylene diamine is prepared in two steps. In the first step 157.5 parts (0.272 mol) of a C36 dibasic acid and 30.8 parts ~0.266 mol) of 1,6-hexane diamine are charged to a reaction vessel and heated with agitation at about 215C. for one hour to form a polyamide resin. During the first 30 minutes the pressure rises to 264 g/cm2 after which time the reaction vessel is ~` 15 vented to reduce the pressure to 158 g/cm2 At the end of one hour the pressure is released and 269 parts of a crystalline polyethylene terephthalate ~M.P.=260C./inherent viscosity 0.147) and 5.9 parts (O.O9S mol) of ethylene glycol are charged to the vessel along with a mlnor amount of an antioxidant. The vessel~ ;
is ~lushed with nitrogen and the mixture is heated;to about 280C.
while maintaining a nitrogen pressure of 70 g/cm2 Ater 0.5 hour the vessel is vented and vacuum applied and the reaction is con-tinued under full vacuum ~0.1 to 5 mm. of mercury) ~or two hours.
At the end of this time the resulting molten poly(ester-amide) is discharged under pressure into a water bath to quench the material. The polymer obtained melts at 185~C. and the inherent viscosity is 0.50. To a stainless steel reactor fitted wit}- an anchor agitator and a jacketed hot oil heating system is added 100 parts by wcight of the poly(ester-ami.de) and heating is begun.
.
. . .
~ 3 3 l~hen the contents have reaclled 250C., agitation is l~egun at 60 rpm and 100 parts by weight dry ~luminum powclcr ~lcoa Atomized Powdcr ]23) is fed into the mass at a rate of 10 parts by weight per minute. The agitatioll is continued and the tem-perature raised to 266C. undcr a nitrogen blanket. Agitationis contiTIue~l for lS minutes ater tlle secolld addition is com-leted and the moltell mass :is dischal~ged ullder slight N2 pressure ~70 g/ctll2 ) tluenchcd in a bath, ground and redried. This material is used to as a hot melt to fill dents and orifices in large metal structures. Ater application it is cooled to room temperature, sanded smooth with 80 grit tungste~n carbide abrasive and painted with an automotive topcoat. ~o "telegraphing" is observed.
Into a sigma-bladed mixer heated by a hot oil external jacket is placed 5.0 parts by weight polytester-amide) of Example 1. Heat is applied and at 216C. agitation is begun. When the mass is molten, 5.0 parts by weight of aluminum powder of average particle size 15 to 19 microns, sold by the Aluminum Company of ; 20 America under the tradename Alcoa Atomized Powder No. 123) is . .
fed over a period of 10 minutes. After addition is completed, heating and agitation is continued for 15 minutes. At this point heating is stopped and under agitation cooling is begun. With agitation under cooling the molten mass becomes friable and breaks up into free flowing aggregate mixture ranging in size from 1/16" to 1/2". This material is sui~able for application as an adhesive or body filling compound when remelted.
~3~33 A preblended mi.xture of 100 parts of the block copoly(ester-amide~ of Example 1 and 100 parts of aluminum powder (~lcoa Powder No. 123) is fed from a hoppcr continuously into a Farrel Continuous ~li.xer whosc temperature controls are set at 216C. Thc mass is continuollsly discharged (estimated ho]d up t:ime 8-10 mi.nut.es) on a cooled conveyer belt and ground.
Alternately the extrllded ribbon is conveyed into a cooling bath, air blown, dried and ground in conventional grinding equipment. The free flowing aggregate is suitable for use as an adhesive and/or void filling compound when remelted and _ applied.
. _ These examples show the effect of varying the filler content of the poly(ester-amide) adhcsive composition. The poly(ester-amide) of Example 1 is blended in the manner set forth in Example 1, with 50, 150 and 20Q parts of Alcoa Atomized Powder No. 123 per 100 parts of poly(ester-amide) respectiveIy.
The data are presented in Table 1.
- 1 5 ~
~ .
.
.
3~333 TABI,~ 1 Block Copoly(es~er-clmide) Filled with Atomi~ed ~luminum Fll].er Parts per Melt 100 parts Vis~osity Melt Creep Sand-EXAMPLE Poly(ester- 10- c~s, Stability Resistance ability alllidc) 4 sec~ 175~C 205C
1 100 35 Stable Pass Pass Pass
The s~cond co~nponent of the adhesive composition is a finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc. The metal powdcr is substantially uniformly dispersecl in the poly(~ster-amid0). It m~y be of number average particle size in the range of 0.2 micron to 150 micron and is preferably of number average particlc size ;n the range of 4 to 100 micron.
The preferred metal filler is atomized aluminum particularly when the adhesive composition is used for cavity filling since it allows the hot melt composition to be readily smoothed and burnished when it is sanded. In general,plate-like, acicular, or multi-faceted granular powdered metals are unsatisfactory, surprisingly causing high viscosity in the hot melt and "blinding"
or filling and occlusion of sand paper when the filled composition is sanded.
The amount of metal po~der which is dispersed in the poly(ester-amide) is sufficient to improve the high temperature creep resistance without causing unmanageable rheology. It is preferably in the range of about 30 to about 7U parts by weight of metal powder dispersed in about 70 to about 30 parts by weight of poly(ester-amide). The melt viscosity of the hot melt composition containing the metal iller is preferably less than about 150,000 centipoises at a temperature of 232C. and a shear rate of 3-4 sec. measured in a Brookfield Thermocel Unit Model HBT. Above 150,000 centipoise melt viscosity, the hot melt is difficult to apply and spread, and tends to be dragged from the point of application.
Creep resistance of the filled poly(ester-amide) com-positions of the present invention is determined by observing .
.
~3~333 the sag of a 10 to 15 ~ram sample of the compositi~n placed on an alulninum plane inclined at 60 to the vertical. Thc obser-vations are carried out at 175 and 205C. Creep or sag in less than 60 minutes at the designated temperature is recorded as a failure to meet the test.
Lap bond l:ens;le strengt}l is de~.ermined by AST~I Test Metllod D-1002-72. A mil~imulll of 100 kg per sq. cm. is preferred.
Sandability of the filled compositions is determined by applying the compasition as a hot melt to a smooth steel panel 7.5 cm. x 22.5 cm. to provide a strip 4 cm. wide and in the range of 25 to 250 microns thick. The panel is cooled to room tempera-ture and a disc sander, 12.5 cm. diameter, with 80 grit medium tungsten carbide abrasive, is applied to the composition at 1000 rpm to smooth and feather the composition. I the surface of the composition becomes smooth enough to accept paint without '-'telegraphing"or showing a difference in refIectivity between the painted steel and the painted composition, and without blinding or blocking the abrasive surface of the sander, the composition , is rated sandable.
When the hot melt composition is formed by mixing the filler with the melted polymer, a good mix is considered to have been obtained if the filler particles are evenly distribu~ed throughout the melt. In poor mlxes, the filler particles are , not adequately wet by the melt, and are not evenly distributed Z5 remaining aggregated within the melt. Melt stability of the mix is determined by maintaining the mix at 216C. for two hours.
If ths melt viscosity changes less than ~10 percent during this time, the mix is considered to have melt stability.
:`
.
- - ~
~ 3 3 Tn addition to improving t~le creep resis~ance of the poly(~ster-amide) component, the metallic component improves the rate of melting of tlle adhcsive composition, allows the composition to be applicd and spread molc easily wit~l less pressure, imp~rts longer "opell" timc bct~een application of the hot melt and closing o~ tlle bond and higher "green" strength or aster onset of bond strength, and reduces the degree of shrinkage of the adhesive composition when lt is cooled from the hot melt te~perature to ambient temperature. The cost of the composition is also considerably reduced. When the composi-tion is used to fill cavities, it can be readily sanded as dis-cussed above, withstands extremes of temperature and humidity, is exceptionally solvent resistant and is readily painted without absorbing solven~, swelling, and blistering.
The hot melt adhesive compositions of the present invention find widespread utility where~er hot melt adhesives are used. They are especially valuable in those applications where resistance to creep at elevated temperatures is a necessary requirement. The adhesive compositions of the present invention may be used to great advantage to bond a variety of substrates including metal, glass, synthetic and natural textiles, leathers, synthetic polymeric sheet material, wood, paper, etc.
The present invention also includes the concept of incorporating various ingredients into the poly~ester-amide) resins of the present invention in order to improve processing and/or performance of these materials. These additives and adjuncts include antioxidants 9 thermal stabilizers~ extenders, dyes, pigments, adhesion promoters, plasticizers, etc.
.
~ ~ 3~ 3 ~
The following examples are sct for~h in illustration of this invention and should not be construed as a limitation thereof. Unless otllerwise ind;cated, all parts and percentages are by weight.
EXAM_L~ I
A block copolymel which is appro~imately 60 percen~
by weight crystalline polyethylene terepht}lalate segments and 40 percent by weight amorphous polyamide made from dimcr acid and hexamethylene diamine is prepared in two steps. In the first step 157.5 parts (0.272 mol) of a C36 dibasic acid and 30.8 parts ~0.266 mol) of 1,6-hexane diamine are charged to a reaction vessel and heated with agitation at about 215C. for one hour to form a polyamide resin. During the first 30 minutes the pressure rises to 264 g/cm2 after which time the reaction vessel is ~` 15 vented to reduce the pressure to 158 g/cm2 At the end of one hour the pressure is released and 269 parts of a crystalline polyethylene terephthalate ~M.P.=260C./inherent viscosity 0.147) and 5.9 parts (O.O9S mol) of ethylene glycol are charged to the vessel along with a mlnor amount of an antioxidant. The vessel~ ;
is ~lushed with nitrogen and the mixture is heated;to about 280C.
while maintaining a nitrogen pressure of 70 g/cm2 Ater 0.5 hour the vessel is vented and vacuum applied and the reaction is con-tinued under full vacuum ~0.1 to 5 mm. of mercury) ~or two hours.
At the end of this time the resulting molten poly(ester-amide) is discharged under pressure into a water bath to quench the material. The polymer obtained melts at 185~C. and the inherent viscosity is 0.50. To a stainless steel reactor fitted wit}- an anchor agitator and a jacketed hot oil heating system is added 100 parts by wcight of the poly(ester-ami.de) and heating is begun.
.
. . .
~ 3 3 l~hen the contents have reaclled 250C., agitation is l~egun at 60 rpm and 100 parts by weight dry ~luminum powclcr ~lcoa Atomized Powdcr ]23) is fed into the mass at a rate of 10 parts by weight per minute. The agitatioll is continued and the tem-perature raised to 266C. undcr a nitrogen blanket. Agitationis contiTIue~l for lS minutes ater tlle secolld addition is com-leted and the moltell mass :is dischal~ged ullder slight N2 pressure ~70 g/ctll2 ) tluenchcd in a bath, ground and redried. This material is used to as a hot melt to fill dents and orifices in large metal structures. Ater application it is cooled to room temperature, sanded smooth with 80 grit tungste~n carbide abrasive and painted with an automotive topcoat. ~o "telegraphing" is observed.
Into a sigma-bladed mixer heated by a hot oil external jacket is placed 5.0 parts by weight polytester-amide) of Example 1. Heat is applied and at 216C. agitation is begun. When the mass is molten, 5.0 parts by weight of aluminum powder of average particle size 15 to 19 microns, sold by the Aluminum Company of ; 20 America under the tradename Alcoa Atomized Powder No. 123) is . .
fed over a period of 10 minutes. After addition is completed, heating and agitation is continued for 15 minutes. At this point heating is stopped and under agitation cooling is begun. With agitation under cooling the molten mass becomes friable and breaks up into free flowing aggregate mixture ranging in size from 1/16" to 1/2". This material is sui~able for application as an adhesive or body filling compound when remelted.
~3~33 A preblended mi.xture of 100 parts of the block copoly(ester-amide~ of Example 1 and 100 parts of aluminum powder (~lcoa Powder No. 123) is fed from a hoppcr continuously into a Farrel Continuous ~li.xer whosc temperature controls are set at 216C. Thc mass is continuollsly discharged (estimated ho]d up t:ime 8-10 mi.nut.es) on a cooled conveyer belt and ground.
Alternately the extrllded ribbon is conveyed into a cooling bath, air blown, dried and ground in conventional grinding equipment. The free flowing aggregate is suitable for use as an adhesive and/or void filling compound when remelted and _ applied.
. _ These examples show the effect of varying the filler content of the poly(ester-amide) adhcsive composition. The poly(ester-amide) of Example 1 is blended in the manner set forth in Example 1, with 50, 150 and 20Q parts of Alcoa Atomized Powder No. 123 per 100 parts of poly(ester-amide) respectiveIy.
The data are presented in Table 1.
- 1 5 ~
~ .
.
.
3~333 TABI,~ 1 Block Copoly(es~er-clmide) Filled with Atomi~ed ~luminum Fll].er Parts per Melt 100 parts Vis~osity Melt Creep Sand-EXAMPLE Poly(ester- 10- c~s, Stability Resistance ability alllidc) 4 sec~ 175~C 205C
1 100 35 Stable Pass Pass Pass
4 50 28 Stable Pass Pass Marginal 150 56 Stable Pass Pass Pass 6 200 ~100 Stable Pass Pass Pass 0 0 20 Stable Fail Pail Fail :
.
.
.
3~3~3 EX~MPLES 7-8 In thesc examples, copoly(ester-amide) filled with flake aluminum is prcpared and compared with copoly(ester-amide) illed with atomized a:lumillum, The poly~ester-am;de) S of ~xample 1 is b1eTICIed Witll :Eiller in t.he manner set ~orth in Fxample 1. The <lata are prescnted in Table 2. The ~lake aluminums o:E Bxamp].es 7. and 8 are produced by Reynolds and sold under the tradenames IP75 Flake Aluminum 40XD and 3XD
respectively and have average particle sizes less than 44 microns. Extremely high melt viscosi.ty is obtained even at low concentration of iller.
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, E:~MI~,ES 9-16 Th~se examples set fort}l a.compari.son between copoly(ester-amide) fi.lled with inorganic mineral pigments and witll atomized aluminum. T}le poly(ester-amide) of Example 1 is blended with fi.ller in tlle manner set forth iTI EXalllple 1. The data are presented in Table 3. In generc1.1 the inorg~nic ~illers telld to bc incompat~.ble, to gi.ve higll vi.scosity, poor mix sta~ility and poor s~ln(lability. Barium sulate demonstrates a urther disadvantage, namely instability at~the hot melt mixing temperature and evolution of acrid fumes of sulfur trioxide.
The oleophilic clay of Examples 9 and 10 is supplied by Georgia Kaolin Company under the Tradename Kaogan 45.
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o : u~ o In 3l~3 X~lPI,P.~S 17 25 These examples arc prepared by filling commercially avai.la`ble polyester and polyamicle hot melt adllesives with atomized aluminum ~owder (~lcocl ~tomized Powder No. 123) in the manner set fortl) in }.xample 1. The data arc presented in Tablo ~. The we:i.gllt rat.io o:~ polylllel t:o 111er is 1:1. The data show that ColllpOsitiolls containillg commerc:ial polyesters and polyamicles generally ~ail. the crcep test and the sandabi-lity test and that those which mar~inally pass the sandability test and the creep test are o such high viscosity that they are dif~icult to apply.
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3~3~3 EX~MPLES 7-8 In thesc examples, copoly(ester-amide) filled with flake aluminum is prcpared and compared with copoly(ester-amide) illed with atomized a:lumillum, The poly~ester-am;de) S of ~xample 1 is b1eTICIed Witll :Eiller in t.he manner set ~orth in Fxample 1. The <lata are prescnted in Table 2. The ~lake aluminums o:E Bxamp].es 7. and 8 are produced by Reynolds and sold under the tradenames IP75 Flake Aluminum 40XD and 3XD
respectively and have average particle sizes less than 44 microns. Extremely high melt viscosi.ty is obtained even at low concentration of iller.
_ , -17- ~ -~
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' ' ':~. : -' . . . .
, E:~MI~,ES 9-16 Th~se examples set fort}l a.compari.son between copoly(ester-amide) fi.lled with inorganic mineral pigments and witll atomized aluminum. T}le poly(ester-amide) of Example 1 is blended with fi.ller in tlle manner set forth iTI EXalllple 1. The data are presented in Table 3. In generc1.1 the inorg~nic ~illers telld to bc incompat~.ble, to gi.ve higll vi.scosity, poor mix sta~ility and poor s~ln(lability. Barium sulate demonstrates a urther disadvantage, namely instability at~the hot melt mixing temperature and evolution of acrid fumes of sulfur trioxide.
The oleophilic clay of Examples 9 and 10 is supplied by Georgia Kaolin Company under the Tradename Kaogan 45.
`
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o : u~ o In 3l~3 X~lPI,P.~S 17 25 These examples arc prepared by filling commercially avai.la`ble polyester and polyamicle hot melt adllesives with atomized aluminum ~owder (~lcocl ~tomized Powder No. 123) in the manner set fortl) in }.xample 1. The data arc presented in Tablo ~. The we:i.gllt rat.io o:~ polylllel t:o 111er is 1:1. The data show that ColllpOsitiolls containillg commerc:ial polyesters and polyamicles generally ~ail. the crcep test and the sandabi-lity test and that those which mar~inally pass the sandability test and the creep test are o such high viscosity that they are dif~icult to apply.
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~: ;Z u) h S~ h h a~ ~ 6~ a) o o 0 a~
U~ ~Y ~~ ~ ~ ~ ~1 ~ rl~ rl ~ rl ~ rl H æ ~ ~
P.l ~ Op~ 1 ~Ir~ l r~l r~l r-l r~
. O P~ r-l O O O ~0 ~ ~ ~~: ~0 , . ~Ll ~ ~: ' ' r-l ~ O C~ O r~
~L~ r-l r~ 1 ~ Nt~l r~ , - 2 ~. -
Claims (30)
1. An adhesive composition comprising:
a) from about 70 to about 30 parts by weight of a poly(ester-amide) block copolymer melting in the range of about 155°C. to about 225°C. having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine containing 2 to 10 carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
a) from about 70 to about 30 parts by weight of a poly(ester-amide) block copolymer melting in the range of about 155°C. to about 225°C. having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine containing 2 to 10 carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
2, The adhesive composition of claim 1 wherein the polyester segment is selected from the group consisting of poly (ethylene-terephthalate), co-poly(butylene-terephthalate)-(ethylene terephthalate), co-poly(ethylene--terephthalate)-(ethylene-isophthalat) and co-poly(ethylene-terephthalate)-(propylene-terephthalate).
3. The adhesive composition of claim 1 wherein the diamine is hexamethylene diamine.
4. The adhesive composition of claim 1 having a 4. The adhesive composition of claim 1 having a melt viscosity at 232°C. of less than about 150,000 centipoise at a shear rate of 4 sec. -1.
5. The adhesive composition of claim 1 wherein the polyester segment prior to incorporation in the polyesteramide has an inherent viscosity at 25°C. in the range of about 0.05 to about 0.70 measured as a 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane and a melting point in the range of about 180° to about 270°C.
6. The adhesive composition of claim 1 wherein the poly(ester-amide) has an inherent viscosity at 25°C. in the range of from 0.35 to about 0.95 measured as a 0.5 gram solu-tion in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane.
7. The adhesive composition of claim 1 wherein the spheroidal metal powder has a particle size in the range of about 0.2 to about 150 microns.
8. An adhesive composition comprising:
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity in the range of about 0.35 to about 0.95 and of melt-ing point in the range of about 155°C. to about 225°C., having from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly (butylene terephthalate)-(ethylene terephthalate), co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene terephthalate) which prior to incorporation in the poly (ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an aliphatic or alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being determined at 25°C. with an 0.5 gram solution in 100 ml.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about 100 microns.
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity in the range of about 0.35 to about 0.95 and of melt-ing point in the range of about 155°C. to about 225°C., having from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly (butylene terephthalate)-(ethylene terephthalate), co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene terephthalate) which prior to incorporation in the poly (ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an aliphatic or alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being determined at 25°C. with an 0.5 gram solution in 100 ml.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about 100 microns.
9. The adhesive composition of claim 8 wherein the diamine is hexamethylene diamine.
10. The adhesive composition of claim 8 having a melt viscosity at 232°C. of less than about 150,000 centipoise at a shear rate of 4 sec.-l.
11. A substrate coated with an adhesive composition wherein the adhesive composition comprises:
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer melting in the range of about 155°C. to about 225°C having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one ali-phatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicar-boxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from an ali-phatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine con-taining 2 to 10 carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer melting in the range of about 155°C. to about 225°C having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one ali-phatic or alicyclic diol having from 2 to 10 carbon atoms and at least one alicyclic or aromatic dicar-boxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from an ali-phatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine con-taining 2 to 10 carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
12. The substrate of claim 11 wherein the polyester segment of the poly(ester-amide) is selected from the group con-sisting of poly(ethylene-terephthalate), co-poly(butylene-terephthalate)-(ethylene-terephthalate), co-poly(ethylene-terephthalate)-(ethylene-isophthalate and co-poly(ethylene-terephthalate)-(propylene terephthalate).
13. The substrate of claim 11 wherein the diamine of the amide segment of the poly(ester-amide) is hexamethylene diamine.
14. The substrate of claim 11 wherein the melt vis-cosity of the adhesive composition at 232°C. is less than about 150,000 centipoise at a shear rate of 4 sec.-l.
15. The substrate of claim 11 wherein the polyester segment prior to incorporation in the poly(ester-amide) has an inherent viscosity at 25°C. in the range of about 0.05 to about 0.70 measured as an 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane and a melting point in the range of about 180° to about 270°C.
16. The substrate of claim 11 wherein the poly(ester-amide) has an inherent viscosity at 25°C. in the range of from 0.35 to about 0.95 measured as an 0.5 gram solution in 100 ml.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane.
17. The substrate of claim 11 wherein the spheroidal metal powder has a particle size in the range of about 0.2 to about 150 microns.
18. A substrate coated with an adhesive composition wherein the adhesive composition comprises:
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity on the range of about 0.35 to about 0.95 and of melt-ing point in the range of about 155°C. to about 225°C., having from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly (butylene terephthalate-ethylene terephthalate, co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene terephthalate) which prior to incorporation in the poly(ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an aliphatic or ;alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being deter-mined at 25°C. with an 0.5 gram solution in 100 ml.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about 100 microns
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity on the range of about 0.35 to about 0.95 and of melt-ing point in the range of about 155°C. to about 225°C., having from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly (butylene terephthalate-ethylene terephthalate, co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene terephthalate) which prior to incorporation in the poly(ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an aliphatic or ;alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being deter-mined at 25°C. with an 0.5 gram solution in 100 ml.
of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about 100 microns
19. The substrate of claim 18 wherein the diamine of the amide segment of the poly(ester-amide) is hexamethylene diamine.
20. The substrate of claim 18 wherein the melt viscosity of the adhesive composition at 232°C. is less than about 150,000 centipoise at a shear rate of 4 sec.-1.
21 In a method of filling a cavity in a substrate which comprises applying excess adhesive composition as a hot melt into the cavity, cooling the adhesive composition below its crystallization temperature, and sanding the adhesive composition to provide a surface even with the surrounding substrate, the improvement wherein the adhesive composition comprises:
a) from about 70 to about 30 parts by weight of a poly(ester-amide) block copolymer melting in the range of about 155°C. to about 225°C. having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 per-cent by weight of amorphous polyamide segments derived from an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine containing 2 to lO
carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
a) from about 70 to about 30 parts by weight of a poly(ester-amide) block copolymer melting in the range of about 155°C. to about 225°C. having from about 30 to about 70 percent by weight of crystalline polyester segments derived from at least one aliphatic or alicyclic diol having 2 to 10 carbon atoms and at least one alicyclic or aromatic dicarboxylic acid having from 8 to 20 carbon atoms, and from about 70 to about 30 per-cent by weight of amorphous polyamide segments derived from an aliphatic polycarboxylic acid containing at least 40 weight percent of a C18 to C54 polycarboxylic acid and an aliphatic or alicyclic primary diamine containing 2 to lO
carbon atoms; and b) from about 30 to about 70 parts by weight of finely divided spheroidal metal powder selected from the group consisting of aluminum, iron, mild steel, stainless steel and zinc.
22, The method of claim 21 wherein the polyester segment is selected from the group consisting of poly(ethylene-terephthalate), co-poly(butylene-terephthalate)-(ethylene-terephthalate), co-poly(ethylene-terephthalate)-(ethylene-isophthalate) and co-poly(ethylene terephthalate)-(propylene-terephthalate).
23. The method of claim 21 wherein the diamine of the amorphous polyamide segments of the poly(ester-amide) is hexamethylene diamine.
24. The method of claim 21 wherein the adhesive com-position has a melt viscosity at 232°C of less than about 150,000 centipoise at a shear rate of 4 sec-1.
25. The method of claim 21 wherein the polyester seg-ment prior to incorporation in the poly(ester-amide) component of the adhesive composition has an inherent viscosity at 25°C.
in the range of about 0.05 to about 0.70 measured as a 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloro-ethane and a melting point in the range of about 180° to about 270°C.
in the range of about 0.05 to about 0.70 measured as a 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloro-ethane and a melting point in the range of about 180° to about 270°C.
26. The method of claim 21 wherein the poly(ester-amide) component of the adhesive composition has an inherent viscosity at 25°C. in the range of from 0.35 to about 0.95 measured as a 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane.
27. The method of claim 21 wherein the spheroidal metal powder has a particle size in the range of about 0.2 to about 150 microns.
C-06-041s
C-06-041s
28. In a method of filling a cavity in a substrate which comprises applying excess adhesive composition as a hot melt into the cavity, cooling the adhesive composition below its crystallization temperature,and sanding the adhesive com-position to provide a surface even with the surrounding sub-strate, the improvement wherein the adhesive composition comprises:
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity in the range of about 0.35 to about 0.95 and of melting point in the range of about 155°C. to about 225°C., having -from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly(butylene terephthalate)-(ethylene terephthalate), co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene tereph-thalate) which prior to incorporation in the poly(ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an a1i-phatic or alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being determined at 25°C. with an 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about l00 microns.
a) from about 70 to about 30 parts by weight of a poly (ester-amide) block copolymer of inherent viscosity in the range of about 0.35 to about 0.95 and of melting point in the range of about 155°C. to about 225°C., having -from about 30 to about 70 percent by weight of crystalline polyester segments selected from the group consisting of poly(ethylene-terephthalate), co-poly(butylene terephthalate)-(ethylene terephthalate), co-poly(ethylene-terephthalate)-(ethylene isophthalate) and co-poly(ethylene terephthalate)-(propylene tereph-thalate) which prior to incorporation in the poly(ester-amide), have an inherent viscosity in the range of about 0.05 to about 0.70 and a melting point in the range of about 180 to about 270°C., and from about 70 to about 30 percent by weight of amorphous polyamide segments derived from a C36 dibasic acid and an a1i-phatic or alicyclic diamine containing from 2 to 10 carbon atoms, the inherent viscosities being determined at 25°C. with an 0.5 gram solution in 100 ml. of a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of symm-tetrachloroethane; and b) from about 30 to about 70 parts by weight of spheroidal aluminum powder of particle size in the range of about 4 to about l00 microns.
29, The method of claim 28 wherein -the diamine of the amorphous polyamide segments of the poly(ester-amide) is hexamethylene diamine.
30. The method of claim 28 wherein the adhesive composition has a melt viscosity at 232°C. of less than about 150,000 centipoise at a shear rate of 4- sec-1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US654,490 | 1976-02-02 | ||
| US05/654,490 US4097445A (en) | 1976-02-02 | 1976-02-02 | Poly(ester-amide) hot melt adhesives containing spheroidal metal powders |
| US654,679 | 1976-02-02 | ||
| US05/654,679 US4073973A (en) | 1976-02-02 | 1976-02-02 | Cavity-filling with a poly(ester-amide) hot melt adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1103833A true CA1103833A (en) | 1981-06-23 |
Family
ID=27096758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,799A Expired CA1103833A (en) | 1976-02-02 | 1977-02-01 | Poly(ester-amide) hot melt adhesive composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5294334A (en) |
| AU (1) | AU510740B2 (en) |
| CA (1) | CA1103833A (en) |
| DE (1) | DE2704089A1 (en) |
| FR (1) | FR2339661A1 (en) |
| IT (1) | IT1077501B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111196914A (en) * | 2018-11-20 | 2020-05-26 | 上海天洋热熔粘接材料股份有限公司 | Polyesteramide hot melt adhesive and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009937B1 (en) * | 1978-10-02 | 1983-10-12 | Monsanto Company | Block copolymer hot melt adhesive compositions, a method of filling a cavity therewith, and a substrate with a cavity filled with such a composition |
| DE2966830D1 (en) * | 1978-10-04 | 1984-04-26 | Monsanto Co | Block copolymer hot melt adhesive compositions, a method of filling a cavity in a substrate therewith, and a substrate with a cavity filled with such a composition |
| EP0009951B1 (en) * | 1978-10-04 | 1984-03-21 | Monsanto Company | A hot melt adhesive composition and a process for filling a cavity in a substrate with this composition |
| EP0009950B1 (en) * | 1978-10-04 | 1984-04-18 | Monsanto Company | Block copolymer hot melt adhesive composition and method of filling a cavity |
| US4485233A (en) * | 1984-02-27 | 1984-11-27 | Union Camp Corporation | Poly(ester-amide) hot-melt adhesives |
| FR2614034B1 (en) * | 1987-04-17 | 1992-06-26 | Picardie Lainiere | TEXTILE ADHESIVE. PROCESS FOR MANUFACTURING TEXTILE REINFORCEMENT AND FABRIC OBTAINED |
-
1977
- 1977-02-01 AU AU21796/77A patent/AU510740B2/en not_active Expired
- 1977-02-01 IT IT19850/77A patent/IT1077501B/en active
- 1977-02-01 CA CA270,799A patent/CA1103833A/en not_active Expired
- 1977-02-01 FR FR7702767A patent/FR2339661A1/en active Granted
- 1977-02-01 JP JP1062077A patent/JPS5294334A/en active Pending
- 1977-02-01 DE DE19772704089 patent/DE2704089A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111196914A (en) * | 2018-11-20 | 2020-05-26 | 上海天洋热熔粘接材料股份有限公司 | Polyesteramide hot melt adhesive and preparation method thereof |
| CN111196914B (en) * | 2018-11-20 | 2022-02-18 | 上海天洋热熔粘接材料股份有限公司 | Polyesteramide hot melt adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2339661B1 (en) | 1982-05-21 |
| DE2704089A1 (en) | 1977-08-04 |
| IT1077501B (en) | 1985-05-04 |
| AU2179677A (en) | 1978-08-10 |
| JPS5294334A (en) | 1977-08-08 |
| AU510740B2 (en) | 1980-07-10 |
| FR2339661A1 (en) | 1977-08-26 |
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