阅读说明：本技术 双组分无溶剂粘着剂组合物 (Two-component solventless adhesive composition ) 是由 李拓奇 J·J·祖潘奇克 M·M·扬基 P·G·克拉克 T·施密特 河本健 李文文 于 2020-03-04 设计创作，主要内容包括：本公开提供一种双组分无溶剂粘着剂组合物。所述双组分无溶剂粘着剂组合物含有(A)异氰酸酯组分和(B)含有聚酯-酰胺聚碳酸酯多元醇的多元醇组分的反应产物。本公开还提供一种形成双组分无溶剂粘着剂组合物的方法。(The present disclosure provides a two-part solventless adhesive composition. The two-component solventless adhesive composition contains the reaction product of (a) an isocyanate component and (B) a polyol component containing a polyester-amide polycarbonate polyol. The present disclosure also provides a method of forming a two-part solventless adhesive composition.)

1. A two-part solventless adhesive composition comprising the reaction product of:

(A) an isocyanate component; and

(B) a polyol component comprising a polyester-amide polycarbonate polyol.

2. The two-part solventless adhesive composition of claim 1 wherein the polyol component further comprises a phosphate-terminated polyol.

3. The two-component solventless adhesive composition of claim 1 or 2 wherein the polyester-amide polycarbonate polyol has a number average molecular weight (Mn) of 500 to 8,000 g/mol.

4. The two-component solvent-free adhesive composition of any of claims 1 to 3, wherein the polyester-amide polycarbonate polyol comprises less than 55 weight percent of species having a weight average molecular weight (Mw) of less than 500 g/mol.

5. The two-part solventless adhesive composition of any one of claims 1-4 wherein the polyol component comprises from 0.5 wt% to 35 wt% phosphate ester terminated polyol based on the total weight of the polyol component.

6. The two-part solvent-free adhesive composition of any one of claims 1 to 5, wherein the isocyanate component is an aliphatic isocyanate prepolymer.

7. The two-part solventless adhesive composition of any one of claims 1-6 wherein the phosphate ester terminated polyol has the structure (C)

Wherein R is⁴Is selected from the group consisting of ether groups and substituted ether groups.

8. A laminate comprising

A first substrate;

a second substrate; and

an adhesive layer interposed between the first substrate and the second substrate, the adhesive layer being formed of the two-component solvent-free adhesive composition according to any one of claims 1 to 7.

9. The laminate of claim 8, wherein the first substrate is a metal foil film and the second substrate is a polypropylene film; and the adhesive strength of the laminate after chemical aging is from 0.50N/2.54cm to 5.0N/2.54 cm.

10. The laminate of claim 8, wherein the first substrate is a polyethylene terephthalate film; and the adhesive strength of the laminate after in-bag boiling test is from 3.5N/2.54cm to 10.0N/2.54 cm.

11. A method of forming a two-part solventless adhesive composition comprising:

(A) Providing a polyol component comprising a polyester-amide polycarbonate polyol;

(B) providing an isocyanate component; and

(C) reacting the polyol component with the isocyanate component to form the two-part solventless adhesive composition.

12. The method of claim 11, comprising providing the polyol component comprising:

(i) the polyester-amide polycarbonate polyol; and

(ii) a phosphate-terminated polyol.

Background

Laminates formed with solventless adhesives often exhibit poor adhesion after chemical aging and/or after high temperature testing such as the in-bag boiling test. Such laminates are not suitable for laminate applications, such as food packaging and deep drawn cans, which require sufficient adhesion for a period of time after exposure to heat and/or chemicals. Insufficient adhesion results in defects in the laminate structure, such as blisters and delamination.

The art recognizes the need for solvent-free adhesives that exhibit sufficient adhesion between substrates after exposure to heat and/or chemicals. Further recognized in the art is a need for adhesive compositions that maintain adhesion in laminated structures exposed to chemical aging, elevated temperatures, and/or in-bag boiling tests.

Disclosure of Invention

The present disclosure provides a two-part solventless adhesive composition. The two-component solventless adhesive composition contains the reaction product of (a) an isocyanate component and (B) a polyol component containing a polyester-amide polycarbonate polyol.

The present disclosure also provides a method of forming a two-part solventless adhesive composition. The method comprises the following steps: (A) providing a polyol component containing a polyester-amide polycarbonate polyol; (B) providing an isocyanate component; and (C) reacting the polyol component with the isocyanate component to form a two-part solventless adhesive composition.

Definition of

Any reference to the periodic table of elements is the periodic table of elements published by CRC Press, inc., 1990-1991. The element groups in this table are referenced by the new notation of the numbered groups.

For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent US version thereof is so incorporated by reference), especially with respect to the definitions in the art (to the extent not inconsistent with any definitions specifically provided in this disclosure) and the disclosure of common general knowledge.

The numerical ranges disclosed herein include all values from the lower and upper values, and include both the lower and upper values. For ranges containing exact values (e.g., ranges of 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two exact values is included (e.g., ranges 1-7 above include subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

The term "alkyl" refers to an organic group derived from an aliphatic hydrocarbon by the deletion of one hydrogen atom from the aliphatic hydrocarbon. The alkyl group can be linear, branched, cyclic, or a combination thereof.

"aryl" refers to an aromatic substituent which may be a single aromatic ring or multiple aromatic rings fused together, covalently linked, or linked to common groups such as methylene or ethylene moieties.

An "amide" is a compound containing an N-C ═ O moiety in the structure.

The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

The terms "comprising", "including", "having" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently enumerated range, except as may be non-essential to operability. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or listed. Unless otherwise specified, the term "or" means the listed members individually as well as in any combination. The use of the singular includes the use of the plural and vice versa.

A "dicarboxylic acid" is a compound containing two carboxyl groups (-COOH).

An "ether group" is a moiety that contains an oxygen atom bonded to two alkyl or aryl groups. "substituted ether group" refers to an ether in which one or more hydrogen atoms bonded to any carbon of the alkyl or aryl group is replaced with another group, such as a phosphate group, a hydroxyl group, and combinations thereof.

A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. The hydrocarbon may be (i) branched or unbranched; (ii) saturated or unsaturated; (iii) cyclic or acyclic; and (iv) any combination of (i) - (iii). Non-limiting examples of hydrocarbons include alkyl, aryl, alkane, alkene, and alkyne.

An "isocyanate" is a compound that contains at least one isocyanate group in the structure. The isocyanate group is represented by the formula: -N ═ C ═ O. A "polyisocyanate" (or "polyfunctional isocyanate") is an isocyanate containing more than one or at least two isocyanate groups. The polyisocyanate having two isocyanate groups is a diisocyanate and the isocyanate having three isocyanate groups is a diisocyanate, and the like. The isocyanate includes aromatic isocyanate, aromatic polyisocyanate, aliphatic isocyanate and aliphatic polyisocyanate.

"polycarbonates" are compounds containing two or more carbonate groups in the same straight chain of atoms.

"polyester" is a compound containing two or more ester linkages in the same atomic straight chain.

"polyester polyols" are compounds of polyesters and polyols. Non-limiting examples of suitable polyester polyols include polycondensates of diols, polyols (e.g., triols, tetraols), dicarboxylic acids, polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids), hydroxycarboxylic acids, lactones, and combinations thereof. The polyester polyols may also be derived from the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols, rather than from the free polycarboxylic acids.

A "polymer" is a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term "homopolymer" (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), as well as the term "interpolymer," which includes copolymers (used to refer to polymers prepared from two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers. Trace amounts of impurities, such as catalyst residues, may be incorporated in and/or within the polymer. It also encompasses all forms of copolymers, such as random, block, and the like. It should be noted that although polymers are often referred to as being "made from" one or more specified monomers "," based on "a particular monomer or monomer type," containing "a particular monomer content, and so forth, in this context, the term" monomer "should be understood to refer to the polymeric remnants of a particular monomer and not to unpolymerized species. In general, polymers herein are referred to as being based on "units" in polymerized form as the corresponding monomers.

A "polyol" is an organic compound containing a plurality of hydroxyl (-OH) groups. In other words, the polyol contains at least two-OH groups. Non-limiting examples of suitable polyols include diols (which contain two-OH groups) and triols (which contain three-OH groups).

A "solventless adhesive" is an adhesive composition that lacks or substantially lacks solvent.

Test method

Acid number (or acid value) is measured according to ASTM D1386/7. Acid number is a measure of the amount of carboxylic acid present in a component or composition. The acid number is the number of milligrams of potassium hydroxide required to neutralize the free carboxylic acid present in one gram of material (e.g., polyol). The unit of the acid value is mg KOH/g.

The glass transition temperature (Tg) was determined by Differential Scanning Calorimetry (DSC) heating curves in which half of The samples had gained liquid heat capacity as described in Bernhard Wunderlich, basic of Thermal Analysis, Thermal Characterization of Polymeric Materials 92,278 and 279(Edith A. Turi eds., 2 nd edition 1997). Baselines are drawn from below and above the glass transition region and are extrapolated through the Tg region. The temperature at which the heat capacity of the sample is half way between these base lines is Tg. The glass transition temperature is given in degrees Celsius (. degree. C.).

The number of hydroxyl groups (or OH number) is a measure of the number of hydroxyl groups present in a component or composition. The OH number is the number of milligrams of potassium hydroxide (mg KOH/g) required to neutralize the hydroxyl groups in one gram of material. The OH number is determined in accordance with DIN 53240.

The viscosity was measured at 25 ℃ and 40 ℃ according to ASTM D2196. The viscosity is reported as mPas.

Gel Permeation Chromatography (GPC)

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a Gel Permeation Chromatography (GPC) system.

"Z-average molecular weight" (Mz) is the third moment average molar mass. Mz is measured using a Gel Permeation Chromatography (GPC) system.

Mw, Mn and Mz are calculated according to the following equations (1) to (3):

wherein Wfi is the weight fraction of the ith component and M_iIs the molecular weight of the ith component. The polydispersity is calculated according to equation (4) below:

the content of species having Mw less than 500g/mol and Mw less than 1000g/mol for the polyol was measured using "GPC One" software from PolymerChar inc using the following equation (5):

f＝∑^jWf_j/∑ⁱWf_iequation (5)

Wherein Wf_jThe weight fraction of the jth component having a molecular weight of less than 500g/mol or 1,000g/mol, respectively.

Adhesive Strength (90 degree T-Peel test)

The adhesive strength was measured according to the 90 ° hand assisted T-peel test. The laminate was cut into 2.54cm wide strips for initial T-peel adhesion strength testing after curing in an oven at 50 ℃ for two days. Thwing Albe equipped with a 50N weight gauge rt^TMThe QC-3A peel tester was operated at a rate of 10 inches/minute. During testing, the tail of the strip was pulled slightly by the finger to ensure that the tail remained oriented 90 ° to the peel direction. The average bond strength (newtons/2.54 centimeters (N/2.54cm)) is determined from a force versus distance curve. Three samples were tested and the average "bond strength" reported.

The adhesive strength is measured one, two, four, seven or fourteen days after the laminate is formed. Adhesive strength was also measured after chemical aging and in-bag boiling tests.

Pouch preparation for in-bag boiling and chemical aging

A 23cm x 30.5cm laminate was folded to provide a 23cm x 15.3cm structure having a first side and a second side. The first side and the second side are each formed from the same laminate. The second substrate (LDPE film or cast polypropylene film) of the first side is in contact with the second substrate (LDPE film or cast polypropylene film) of the second side. The structure has four edges including a folded edge and three open edges. The edges were trimmed on a guillotine to give a folded structure of 12.7cm x 17.8 cm. The two open edges are heat sealed to form a pouch. The heat sealing was carried out at 177 ℃ for 1 second under a hydraulic pressure of 276 kPa. Four to six pouches were made from each example.

Each pouch was filled with 100mL of sauce (a mixture of tomato sauce, vinegar and vegetable oil by 1:1:1 weight) through the remaining open edge. Spraying of sauce onto the heat seal area is avoided to prevent failure of the heat seal. After filling, the edges of the opening are heat sealed in a manner that minimizes air entrapment inside the closed pouch. Each sealed pouch had four sealed edges and an internal void of 10.2cm x 15.2cm (filled with sauce). The integrity of each heat seal was visually checked to ensure that there were no seal defects that would cause the pouch to leak during testing. Pouches with suspected defects were discarded and replaced.

Boiling in the bagFill pan with 2/3 water and boil it. The boiling pot was covered with a lid to minimize water and steam losses. Two to three sachets of each sample were placed separately in boiling water and held inBoiling in water for 30 minutes. The pouch is then removed from the boiling water and visually inspected for openings, bubbling, blistering, delamination, and/or leakage. The pouch was cut open, emptied of sauce and rinsed with soap and water. One or more strips (2.45cm wide) of laminate were cut from the pouches (excluding the heat seal area). The adhesive strength of the laminate was measured according to the 90 ° T-peel test described above. The adhesive strength was measured as soon as possible after emptying the sachets of sauce. The interior of the pouch was visually inspected for defects.

Chemical ageingTwo to three sachets filled with sauce for each sample were placed in a convection oven at a temperature of 60 ℃ for a period of 100 hours. The pouch was then removed from the oven, cooled to room temperature, and visually inspected for openings, bubbling, blistering, delamination, and/or leakage. The pouch was cut open, emptied of sauce and rinsed with water. One or more strips (2.54cm wide) of laminate were cut from the pouches (excluding the heat seal area). The adhesive strength of the laminate was measured according to the 90 ° T-peel test described above. The adhesive strength was measured as soon as possible after emptying the sachets of sauce. The interior of the pouch was visually inspected for defects.

Detailed Description

The present disclosure provides a two-part solventless adhesive composition. The two-component solventless adhesive composition contains the reaction product of (a) an isocyanate component and (B) a polyol component containing a polyester-amide polycarbonate polyol.

A. Isocyanate component

Two-component solventless adhesive compositions contain the reaction product of (a) an isocyanate component (NCO component) and (B) a polyol component.

Non-limiting examples of suitable NCO components include aromatic isocyanates, aliphatic isocyanates, carbodiimide-modified isocyanates, polyisocyanate trimers, polyfunctional isocyanates, isocyanate prepolymers, and combinations thereof.

An "aromatic isocyanate" (or "aromatic polyisocyanate") is an isocyanate containing one or more aromatic rings. Non-limiting examples of suitable aromatic isocyanates include isomers of methylene diphenyl diisocyanate (MDI); modified MDI, such as carbodiimide-modified MDI or allophanate-modified MDI; isomers of toluene-dimerized isocyanate (TDI); isomers of naphthalene-dimer isocyanate (NDI); isomers of phenylene diisocyanate dimer (PDI); and combinations thereof.

An "aliphatic isocyanate" (or "aliphatic polyisocyanate") is an isocyanate that lacks or does not contain aromatic rings. Aliphatic isocyanates include cycloaliphatic isocyanates in which the chemical chain is a ring structure. In one embodiment, the aliphatic isocyanate contains 3, or 4, or 5, or 6 to 7, or 8, 10, 12, 13, or 14, or 15, or 16 carbon atoms in the straight chain, branched chain, or cyclic alkylene residue. Non-limiting examples of suitable aliphatic isocyanates include cyclohexane diisocyanate; methylcyclohexane diisocyanate; ethyl cyclohexane diisocyanate; propylcyclohexane diisocyanate; methyl diethyl cyclohexane diisocyanate; propane diisocyanate; butane diisocyanate; pentane diisocyanate; hexane diisocyanate; heptane diisocyanate; octane diisocyanate; nonane diisocyanate; nonane triisocyanate; decane diisocyanate and decane triisocyanate; undecane diisocyanate and undecane triisocyanate; dodecane diisocyanate and dodecane triisocyanate; isophorone diisocyanate; hexamethylene diisocyanate; diisocyanatodicyclohexylmethane; 2-methylpentane diisocyanate; 2,2, 4-trimethylhexamethylene diisocyanate; 2,4, 4-trimethylhexamethylene diisocyanate; norbornane diisocyanate (NBDI); xylene diisocyanate; isomers, dimers and/or trimers thereof; and combinations thereof.

A "polyisocyanate trimer" is a reaction product prepared by the trimerization of a diisocyanate in the presence of a catalyst. A non-limiting example of a polyisocyanate trimer is the 2,4-TDI trimer (which is available as CAS 26603-40-7).

In one embodiment, the isocyanate is a multifunctional isocyanate. In another embodiment, the polyfunctional isocyanate is selected from the group consisting of diisocyanates, triisocyanates, and combinations thereof. In another embodiment, the polyfunctional isocyanate is a diisocyanate.

An "isocyanate prepolymer" is the reaction product of a polyisocyanate and at least one polyol. The polyisocyanate is bonded to the polyol in a chemical reaction to form an isocyanate prepolymer. Non-limiting examples of suitable polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, carbodiimide-modified polyisocyanates, and combinations thereof. Non-limiting examples of polyols suitable for use in forming the isocyanate prepolymer include polyester polyols, polyether polyols, aliphatic polyols, and combinations thereof. In one embodiment, the isocyanate prepolymer is the reaction product of a polyisocyanate, a polyol, and optionally a catalyst. Non-limiting examples of suitable catalysts include dibutyltin dilaurate, zinc acetate, 2-dimorpholinodiethyl ether, and combinations thereof.

In one embodiment, the isocyanate is an aliphatic isocyanate prepolymer. A non-limiting example of a suitable aliphatic isocyanate prepolymer is MOR-FREE^TMC-33, available from Dow Chemical Company.

The NCO component may comprise two or more embodiments disclosed herein.

B. Polyol component

The two-part solventless adhesive composition contains the reaction product of (A) an NCO component and (B) a polyol component. The polyol component contains a polyester-amide polycarbonate polyol.

Polyester-amide polycarbonate polyols

The polyol component contains a polyester-polycarbonate polyol.

A "polyester-amide polycarbonate polyol" (or "PE-A PC") is a compound that is a polyester, an amide, a polycarbonate, and a polyol. PE-a PC can be prepared by reacting: aliphatic and aromatic diacid monomers (such as Adipic Acid (AA) and isophthalic acid), diol monomers (including aliphatic diol monomers and polyether diol monomers) (such as ethylene glycol, 1, 4-butanediol, 1, 6-Hexanediol (HDO), neopentyl glycol (NPG), and 1, 2-Propanediol (PDO)), carbonate monomers or polycarbonates (such as poly (1, 4-butanediol-carbonate (BDO-PC)), and amide monomers (such as Ethylenediamine (EDA), N' -dimethylethylenediamine (DMEDA), or ethanolamine).

In one embodiment, the PE-A PC is selected from the group consisting of (i) the reaction product of AA, PDO, NPG, HDO, BDO-PC and EDA; (ii) reaction products of AA, PDO, NPG, HDO, BDO-PC and DMDEA; (iii) (iii) the reaction product of AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and EDA (iv) the reaction product of AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and DMDAA; (v) reaction products of AA, PDO, NPG, HDO, BDO-PC and ethanolamine; and (vi) combinations thereof.

In one embodiment, the PE-A PC has the structure (A):

wherein n is 1 or 2 to 5; p is 1 or 2 to 30; m is 1 or 2 to 20;

R¹is selected from- (CH)₂)₄-、

R²Is selected from- (CH)₂)₄-and- (CH)₂)₆-；

R³Is selected from- (CH)₂)₂-、-(CH₂)₄-、-(CH₂)₆-、-(CH₂)₂-O-(CH₂)₂-、-CH₂-C(CH₃)-、-CH₂-CH(CH₃)-CH₂-and-CH₂-C(CH₃)₂-CH₂-；

R⁴Selected from O, NH, NCH₃And NCH₂CH₃；

R⁵Selected from O, NH, NCH₃And NCH₂CH₃(ii) a With the proviso that R⁴And R⁵Are not all O.

In one embodiment, the number average molecular weight Mn of the PE-A PC is from 500g/mol or 1000g/mol to 1700g/mol, or 2000g/mol, or 3000g/mol, or 5000g/mol, or 8000 g/mol; or from 500g/mol to 8000g/mol, or from 1000g/mol to 5000g/mol, or from 1000g/mol to 2000 g/mol.

In one embodiment, the weight average molecular weight Mw of the PE-A PC is from 500g/mol or 2000g/mol to 3500g/mol or 5000 g/mol; or from 500g/mol to 5000g/mol, or from 2000g/mol to 3500 g/mol.

In one embodiment, the Mw/Mn of PE-A PC is from 1.5 or 1.6 to 1.9 or 2.2 or 2.5; or 1.5 to 2.5, or 1.6 to 1.2.

In one embodiment, the acid number of PE-A PC is from 0.01mg KOH/g to 1.6mg KOH/g or 2.0mg KOH/g; or from 0.01mg KOH/g to 2.0mg KOH/g, or from 0.01mg KOH/g to 1.6mg KOH/g.

In one embodiment, the OH number of the PE-A PC is from 100mg KOH/g to 150mg KOH/g or 200mg KOH/g; or from 100mg KOH/g to 200mg KOH/g, or from 100mg KOH/g to 150mg KOH/g.

In one embodiment, the glass transition temperature (Tg) of PE-A PC is-90 ℃, or-80 ℃, or-75 ℃ to-65 ℃, or-60 ℃, or-55 ℃, or-50 ℃; or-90 ℃ to-50 ℃, or-80 ℃ to-55 ℃.

In one embodiment, the PE-A PC has a viscosity at 25 ℃ of from 500 mPas or 1000 mPas to 3000 mPas or 5000 mPas; or from 500 mPas to 5000 mPas, or from 900 mPas to 3000 mPas.

In one embodiment, the PE-A PC has a viscosity at 40 ℃ of from 300 mPas or 350 mPas to 2000 mPas or 4000 mPas; or from 300 to 4000 mPas or from 350 to 2000 mPas.

In one embodiment, the PE-a PC contains less than 55 wt%, or less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 20 wt%, or less than 15 wt%, or less than 10 wt%, based on the total weight of the PE-a PC; or 0 wt%, or 0.01 wt%, or 1 wt% to 10 wt%, or 15 wt%, or 20 wt%, or 30 wt%, or 40 wt%, or 50 wt%, or 55 wt%; or 0 wt.% to 10 wt.% of species having an Mw of less than 500 g/mol. In one embodiment, the PE-a PC contains less than 55 wt%, or less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 26 wt%, based on the total weight of the PE-a PC; or 0 wt%, or 0.01 wt%, or 1 wt% to 26 wt%, or 30 wt%, or 40 wt%, or 50 wt%, or 55 wt%; or 0 wt% to 30 wt% of species having an Mw of less than 1000 g/mol. Without wishing to be bound by any particular theory, it is believed that (i) a low content (i.e., less than 55 wt%) of species having an Mw of less than 500g/mol and/or (ii) a low content (i.e., less than 55 wt%) of species having an Mw of less than 1000g/mol in the PE-a-PC minimizes migration of low molecular weight species in the cured laminating adhesive, which is advantageous for food packaging applications.

In one embodiment, the PE-A PC has one, some, or all of the following characteristics: (i) mn is 500g/mol to 8000g/mol, or 1000g/mol to 2000 g/mol; and/or (ii) an Mw of 500g/mol to 5000g/mol, or 2000g/mol to 3500 g/mol; and/or (iii) Mw/Mn is from 1.5 to 2.5, or from 1.6 to 1.2; and/or (iv) an acid number of from 0.01mg KOH/g to 2.0mg KOH/g, or from 0.01mg KOH/g to 1.6mg KOH/g; and/or (v) an OH number of from 100mg KOH/g to 200mg KOH/g, or from 100mg KOH/g to 150mg KOH/g; and/or (vi) a Tg of-90 ℃ to-50 ℃, or-80 ℃ to-55 ℃; and/or (vii) a viscosity at 25 ℃ of from 500 to 5000 mPa.s, or from 900 to 3000 mPa.s; and/or (viii) a viscosity at 40 ℃ of from 300 to 4000 mPas, or from 350 to 2000 mPas; and/or (ix)0 wt% to 10 wt% of species having a Mw of less than 500 g/mol; and/or (x) from 0 wt% to 30 wt%, based on the total weight of PE-apc, of species having an Mw of less than 1000 g/mol; and/or (xi) has structure (A); and/or (xii) a reaction product selected from: (a) AA, PDO, NPG, HDO, BDO-PC and EDA; (b) AA, PDO, NPG, HDO, BDO-PC and DMDEA; (c) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and EDA; (d) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and DMDEA; (e) AA, PDO, NPG, HDO, BDO-PC and ethanolamine; and (f) combinations thereof.

The PE-a PC may comprise two or more embodiments disclosed herein.

Phosphate-terminated polyols

In addition to PE-a PC, the polyol component may contain a phosphate-terminated polyol.

A "phosphate-terminated polyol" ("PT-PO") is a polyol containing at least one phosphate group having the structure (B):

PT-PO can be prepared by reacting a polyether polyol with a phosphoric acid type acid. The "phosphoric acid type acid" is orthophosphoric acid, a compound prepared by condensing orthophosphoric acid by eliminating water, or a combination thereof. Non-limiting examples of suitable phosphoric acid type acids include pyrophosphoric acid, tripolyphosphoric acid, and polyphosphoric acid (PPA). In one embodiment, the PT-PO is a reaction product of a polyether polyol and PPA.

In one embodiment, PT-PO has the structure (C):

wherein R is⁶Is an ether group or a substituted ether group.

In one embodiment, R⁶Is polyether. In another embodiment, R⁶Containing only carbon atoms, hydrogen atoms, optionally oxygen atoms, and optionally phosphorus atoms.

In one embodiment, R⁶Is selected from C₁-C₁₂₀Ether group, or C₁-C₅₀Ether group, or C₁-C₂₄Ether group, or C₁-C₈Ether group, or C₁-C₆Ether groups, each of which may optionally contain one or more pendant-OH groups and/or one or more pendant structure (B) groups.

In one embodiment, the PT-PO has an OH number of 200mg KOH/g or 250mg KOH/g to 300mg KOH/g or 350mg KOH/g. In one embodiment, the acid number of PT-PO is 5mg KOH/g, or 10mg KOH/g, or 20mg KOH/g to 25mg KOH/g, or 30mg KOH/g, or 50mg KOH/g.

In one embodiment, the viscosity of PT-PO at 25 ℃ is 1000 mPas, or 1500 mPas, or 1700 mPas to 1800 mPas or 2000 mPas.

In one embodiment, the Mn of PT-PO is 500g/mol, or 750g/mol to 1000g/mol, or 1500g/mol, or 2000g/mol, or 5000g/mol or 8000 g/mol. In one embodiment, the Mw of PT-PO is 1000g/mol or 1400g/mol to 1500g/mol, or 2000g/mol, or 3000g/mol, or 5000g/mol or 8000 g/mol.

In one embodiment, the Mw/Mn of PT-PO is 1.5 or 1.8 to 2.0 or 2.5.

In one embodiment, the PT-PO contains less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 27 wt%, based on the total weight of the PT-PO; or 0 wt%, or 0.01 wt%, or 1 wt% to 26 wt%, or 30 wt%, or 40 wt%, or 50 wt%; or 0 wt.% to 30 wt.% of species having an Mw of less than 500 g/mol. In one embodiment, the PT-PO contains less than 55 wt%, or less than 50 wt%, or less than 45 wt%, or less than 42 wt%, based on the total weight of the PT-PO; 0 wt%, or 0.01 wt%, or 1 wt% to 42 wt%, or 45 wt%, or 50 wt%, or 55 wt%; 0 wt.% to 45 wt.% of species having an Mw of less than 1000 g/mol. Without wishing to be bound by any particular theory, it is believed that (i) a low content (i.e., less than 50 wt%) of species having a Mw of less than 500g/mol and/or (ii) a low content (i.e., less than 55 wt%) of species having a Mw of less than 1000g/mol in the PT-PO minimizes migration of low molecular weight species in the cured laminating adhesive.

In one embodiment, the PT-PO has one, some or all of the following characteristics: (i) the OH number is 200mg KOH/g to 350mg KOH/g, 250mg KOH/g to 300mg KOH/g; and/or (ii) an acid number of from 5mg KOH/g to 50mg KOH/g, or from 20mg KOH/g to 30mg KOH/g; and/or (iii) a viscosity at 25 ℃ of from 1000 to 2000 mPas, or from 1700 to 1800 mPas; and/or (iv) Mn from 500g/mol to 8000g/mol, or from 750g/mol to 1000 g/mol; and/or (v) a Mw of 1000g/mol to 8000g/mol, or 1400g/mol to 1500 g/mol; and/or (vi) Mw/Mn is from 1.5 to 2.5, 1.8 to 2.0; and/or (vii)0 wt% to 30 wt% of species having an Mw of less than 500 g/mol; and/or (viii) 0 to 45 wt.% of species having an Mw of less than 1000g/mol, based on the total weight of PT-PO; and/or (viii) has structure (C); and/or (ix) is the reaction product of a polyether polyol and PPA.

Non-limiting examples of suitable PT-POs are the PT-POs disclosed in U.S. patent publication No. 2017/0226391, which is incorporated herein by reference in its entirety.

The PT-PO can comprise two or more embodiments disclosed herein.

Optional additives

The polyol component may contain (iv) optional additives in addition to (i) PE-A PC and (ii) optional PT-PO.

Non-limiting examples of suitable optional additives include polyols, adhesion promoters, chain extenders, catalysts, and combinations thereof.

Non-limiting examples of suitable optional additives are polyols. The polyol can be any polyol disclosed herein, provided that the optional polyol is different from (i) PE-a PC and (ii) PT-PO. The polyols may be compositionally distinct and/or physically distinct from (i) PE-A PC and (ii) PT-PO.

Non-limiting examples of suitable polyols include diols (which contain two-OH groups), triols (which contain three-OH groups), and combinations thereof. Non-limiting examples of suitable diols include 2-methyl-1, 3-propanediol (MPG); 3-methyl-1, 5-pentanediol; ethylene glycol; butanediol; diethylene glycol (DEG); triethylene glycol; polyalkylene glycols, such as polyethylene glycol (PEG); 1, 2-propanediol; 1, 3-propanediol; 1, 3-butanediol; 1, 4-butanediol; 1, 6-hexanediol; and NPG. A non-limiting example of a suitable triol is Trimethylolpropane (TMP).

In one embodiment, the additive is a polyol that is a polyester polyol, a polyether polyol, or a combination thereof. Non-limiting examples of suitable polyether polyols include polypropylene glycol, PEG, polybutylene glycol, polytetramethylene ether glycol, and combinations thereof.

Non-limiting examples of suitable adhesion promoters include aminosilanes (e.g., (3-aminopropyl) triethoxysilane and (3-aminopropyl) trimethoxysilane), epoxysilanes (e.g., (3-glycidyloxypropyl) trimethoxysilane), phosphate esters (e.g., polypropylene glycol based phosphate esters), epoxy resins (e.g., 1, 4-butanediol diglycidyl ether based epoxy resins), and combinations thereof.

Non-limiting examples of suitable chain extenders include glycerol; trimethylolpropane; DEG; propylene glycol; MPG; 3-methyl-1, 5-pentanediol; and combinations thereof.

Non-limiting examples of suitable catalysts include tetra-n-butyl titanate, titanium isopropoxide, zinc sulfate, organotin catalysts (e.g., dibutyltin dilaurate), and combinations thereof.

In one embodiment, the reaction mixture does not include a chain extender.

The optional additives may comprise two or more embodiments disclosed herein.

In one embodiment, the polyol component contains, consists essentially of, or consists of: (i) PE-A PC, (ii) optionally PT-PO and (iii) optionally additives.

In one embodiment, the polyol component contains 65 wt%, or 85 wt%, or 90 wt% to 95 wt% or 100 wt% PE-a PC based on the total weight of the polyol component.

In one embodiment, the polyol component contains 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt% to 95 wt%, or 98 wt%, or 99 wt%, or 99.5 wt% PE-a PC, based on the total weight of the polyol component; and a mutually inverse amount of PT-PO, or 0.5 wt%, or 1 wt%, or 2 wt%, or 5 wt% to 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt% PT-PO. In another embodiment, the polyol component contains from 65 wt% to 99.5 wt%, or from 70 wt% to 99 wt%, or from 75 wt% to 95 wt%, or from 85 wt% to 95 wt% PE-a PC; and 0.5 wt% to 35 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 5 wt% to 15 wt% PT-PO.

In one embodiment, the polyol component has an OH number of 50mg KOH/g, or 100mg KOH/g to 160mg KOH/g, or 200mg KOH/g.

It is understood that the components in each of the components, mixtures, compositions, and layers disclosed herein, including the aforementioned polyol component, sum to 100 weight percent (wt%), based on the total weight of the respective component, mixture, composition, or layer.

The polyol component may include two or more embodiments disclosed herein.

C. Two-component solventless adhesive composition

Two-part solventless adhesive compositions contain (A) an NCO component; and (B) a polyol component comprising PE-A PC and (ii) optionally PT-PO.

The two-part solventless adhesive composition is formed by mixing (a) an NCO component and (B) a polyol component under conditions suitable to react the-NCO groups of the NCO component with the-OH groups of the polyol component. In one embodiment, (a) the NCO component is combined with (B) the polyol component and mixed at a temperature of 15 ℃, or 20 ℃ to 23 ℃, or 25 ℃, or 45 ℃ for a period of 10 minutes to 30 minutes.

In one embodiment, the two-part solventless adhesive composition comprises (a) an NCO component and (B) a polyol component in a weight ratio of isocyanate to polyol of 100:100, or 100:125, or 100:132 to 100:189, or 100:190, or 100:195, or 100:200 on a dry weight basis; or 100:100 to 100:200, or 100:125 to 100:195, or 100:133 to 100: 189.

The two-component solvent-free adhesive composition is devoid or substantially devoid of solvent.

In one embodiment, the two-part solventless adhesive composition comprises, consists essentially of, or consists of the reaction product of:

(A) An NCO component comprising an aliphatic isocyanate prepolymer;

(B) a polyol component containing, consisting essentially of, or consisting of

(i) From 65 wt% to 100 wt%, or from 65 wt% to 99.5 wt%, or from 85 wt% to 95 wt%, based on the total weight of the polyol component, of PE-a PC having one, some, or all of the following characteristics: (a) mn is 500g/mol to 8000g/mol, or 1000g/mol to 2000 g/mol; and/or (b) an Mw of 500g/mol to 5000g/mol, or 2000g/mol to 3500 g/mol; and/or (c) Mw/Mn from 1.5 to 2.5, or from 1.6 to 1.2; and/or (d) an acid number of from 0.01mg KOH/g to 2.0mg KOH/g, or from 0.01mg KOH/g to 1.6mg KOH/g; and/or (e) an OH number of from 100mg KOH/g to 200mg KOH/g, or from 100mg KOH/g to 150mg KOH/g; and/or (f) a Tg of-90 ℃ to-50 ℃, or-80 ℃ to-55 ℃; and/or (g) a viscosity at 25 ℃ of from 500 to 5000 mPas, or from 900 to 3000 mPas; and/or (h) a viscosity at 40 ℃ of from 300 to 4000 mPas, or from 350 to 2000 mPas; and/or (i)0 wt% to 10 wt% of species having an Mw of less than 500 g/mol; and/or (j) from 0 wt% to 30 wt%, based on the total weight of PE-apc, of species having an Mw of less than 1000 g/mol; and/or (k) has structure (A); and/or (l) a reaction product selected from the group consisting of (1) AA, PDO, NPG, HDO, BDO-PC and EDA; (2) AA, PDO, NPG, HDO, BDO-PC and DMDEA; (3) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and EDA; (4) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC and DMDEA; (5) AA, PDO, NPG, HDO, BDO-PC and ethanolamine; and (6) combinations thereof;

(ii) Optionally, from 0.5 wt% to 35 wt%, or from 5 wt% to 15 wt%, based on the total weight of the polyol component, of PT-PO, the PT-PO having one, some, or all of the following characteristics: (a) the OH number is 200mg KOH/g to 350mg KOH/g, or 250mg KOH/g to 300mg KOH/g; and/or (b) an acid number of from 5mg KOH/g to 50mg KOH/g, or from 20mg KOH/g to 30mg KOH/g; and/or (c) a viscosity at 25 ℃ of from 1000 to 2000 mPas, or from 1700 to 1800 mPas; and/or (d) Mn from 500g/mol to 8000g/mol, or from 750g/mol to 1000 g/mol; and/or (e) a Mw of 1000g/mol to 8000g/mol, or 1400g/mol to 1500 g/mol; and/or (f) Mw/Mn is from 1.5 to 2.5, or from 1.8 to 2.0; and/or (g)0 wt% to 30 wt% of species having an Mw of less than 500 g/mol; and/or (h) 0 wt% to 45 wt% of species having an Mw of less than 1000g/mol, based on the total weight of PT-PO; and/or (i) has structure (C); and/or (j) is the reaction product of a polyether polyol and PPA; and

(C) optionally, an additive;

wherein the two-part solventless adhesive composition has a weight ratio of isocyanate to polyol of 100:100 to 100:200 or 100:133 to 100:189 on a dry weight basis.

The two-component solventless adhesive composition may comprise two or more embodiments disclosed herein.

D. Laminate

The present disclosure provides a laminate. The laminate includes a first substrate, a second substrate, and an adhesive layer between the first substrate and the second substrate. The adhesive layer is formed from a two-part solventless adhesive composition.

The two-part solventless adhesive composition may be any of the two-part solventless adhesive compositions disclosed herein.

The laminate includes a first substrate and a second substrate. The first substrate and the second substrate may be the same or different. In one embodiment, the first substrate is the same as the second substrate such that it has the same composition and the same structure.

In one embodiment, the first substrate and the second substrate are different from each other compositionally and/or structurally.

It should be understood that the following description referring to "substrate" refers to the first substrate and the second substrate individually and/or collectively.

A non-limiting example of a suitable substrate is a film. The film may be a monolayer film or a multilayer film. The multilayer film contains two or more layers. For example, the multilayer film may have two, three, four, five, six, seven, eight, nine, ten, eleven, or more layers. In one embodiment, the multilayer film contains only two layers, or only three layers.

In one embodiment, the film is a monolayer film having one and only one layer.

In one embodiment, the film comprises a layer comprising a component selected from the group consisting of: ethylene-based polymers, propylene-based polymers (PP), polyamides (e.g., nylon), polyesters, ethylene vinyl alcohol (EVOH) copolymers, polyethylene terephthalate (PET), Ethylene Vinyl Acrylate (EVA) copolymers, ethylene methyl acrylate copolymers, ethylene ethyl acrylate copolymers, ethylene butyl acrylate copolymers, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ionomers of ethylene acrylic acid, ionomers of methacrylic acid, maleic anhydride grafted ethylene-based polymers, polylactic acid (PLA), polystyrene, metal foil, cellulose, cellophane (cellophane), non-woven fabrics (nonwoven fabric), and combinations thereof. A non-limiting example of a suitable metal foil is aluminum foil. The layers of the multilayer film may be formed from the same components or from different components.

In one embodiment, the film comprises a layer comprising a metal foil.

The substrate and the further film are continuous structures having two opposing surfaces.

In one embodiment, the substrate has a thickness of 5 μm, or 10 μm, or 15 μm, or 20 μm to 25 μm, or 30 μm, or 40 μm, or 50 μm, or 100 μm, or 200 μm, or 300 μm, or 400 μm, or 500 μm.

In one embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a single layer film having a single layer that is an ethylene-based polymer layer, such as Low Density Polyethylene (LDPE), or a propylene-based polymer layer, such as polypropylene.

The first substrate may comprise two or more embodiments disclosed herein.

The second substrate may comprise two or more embodiments disclosed herein.

The two-part solventless adhesive composition is applied between a first substrate and a second substrate, such as using a Nordmecanica Labo Combi laminator.

Non-limiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and spraying.

In one embodiment, the two-part solventless adhesive composition is applied at 1.6 grams per square meter (g/m)²) To 2.0g/m²Is applied between the first substrate and the second substrate.

In one embodiment, the two-part solvent-free adhesive composition is applied uniformly between the first substrate and the second substrate. "uniformly applied" is a layer of the composition that is continuous (uninterrupted) over the surface of the substrate and has the same or substantially the same thickness over the surface of the substrate. In other words, the composition that is uniformly applied to the substrate directly contacts the substrate surface, and the composition is coextensive with the substrate surface.

The two-part solventless adhesive composition and the first substrate are in direct contact with each other. As used herein, the term "direct contact" is a layer configuration in which the substrate is positioned proximate to the two-component solvent-free adhesive composition or layer, and there is no intervening layer or no intervening structure between the substrate and the two-component solvent-free adhesive composition or layer. The two-part solvent-free adhesive composition directly contacts the surface of the first substrate.

The structure comprising the first substrate, the second substrate, and the two-part solvent-free adhesive composition has the following structure (H):

first substrate/two-component solventless adhesive composition/second substrate

Structure (H).

The adhesive layer of structure (H) is formed from a cured two-part solvent-free adhesive composition. The two-part solventless adhesive composition is formed by mixing and reacting (a) an NCO component and (B) a polyol component.

In one embodiment, the two-part solventless adhesive composition is cured in an oven at a temperature of 30 ℃, or 35 ℃ to 40 ℃, or 45 ℃, or 50 ℃.

In one embodiment, the two-part solventless adhesive composition is cured at a temperature of 20 ℃ to 25 ℃ for a period of 1 day to 2 days, or 4 days, or 7 days.

In one embodiment, the structure (H) is cured to form an adhesive layer between the first substrate and the second substrate, thereby forming a laminate. The laminate has the following structure (J): a first substrate/adhesive layer/second substrate structure (J).

The laminate includes a first substrate in direct contact with the adhesive layer and a second substrate in direct contact with the adhesive layer.

In one embodiment, the first substrate is a film having a layer that is a metal foil layer and the second substrate is a monolayer film having a monolayer that is an ethylene-based polymer (such as LDPE). In another embodiment, the laminate has one, some or all of the following properties after curing at 25 ℃: (i) the bond strength after two days is 1.5N/2.54cm, or 1.6N/2.54cm to 4.6N/2.54cm, or 9.0N/2.54 cm; and/or (ii) an adhesive strength after four days of 2.0N/2.54cm, or 2.5N/2.54cm to 6.0N/2.54cm, or 9.0N/2.54 cm; and/or (iii) an adhesive strength after seven days of 2.5N/2.54cm, or 2.6N/2.54cm to 4.2N/2.54cm, or 8.0N/2.54 cm; and/or (iv) a bond strength after fourteen days of 2.0N/2.54cm, or 2.5N/2.54cm to 4.0N/2.54cm, or 60.0N/2.54 cm; and/or (v) a bond strength after in-bag boiling test of 1.5N/2.54cm, or 1.6N/2.54cm to 3.1N/2.54cm, or 8.0N/2.54 cm; or 1.5N/2.54cm to 8.0N/2.54 cm. In another embodiment, the laminate has one, some or all of the following properties after curing at 45 ℃: (i) the adhesive strength after one day is 3.0N/2.54cm to 4.5N/2.54cm, or 7.0N/2.54 cm; and/or (ii) an adhesive strength after seven days of from 2.9N/2.54cm to 6.0N/2.54cm, or 8.0N/2.54 cm; and/or (iii) a bond strength after fourteen days of from 2.5N/2.54cm to 4.0N/2.54cm, or 7.0N/2.54 cm; and/or (iv) a bond strength after in-bag boiling test of from 1.4N/2.54cm to 5.5N/2.54cm, or 8.0N/2.54 cm; and/or (v) an adhesive strength after chemical ageing of from 0.15N/2.54cm, or from 0.19N/2.54cm to 0.50N/2.54cm, or 3.0N/2.54 cm.

In one embodiment, the first substrate is a film having a layer that is a metal foil layer and the second substrate is a single layer film having a single layer that is a propylene-based polymer (such as polypropylene or further cast polypropylene). In another embodiment, the laminate has one, some or all of the following properties after curing at 25 ℃: (i) the bond strength after two days is 0.01N/2.54cm, or 0.03N/2.54cm, or 1.0N/2.54cm to 5.5N/2.54cm, or 8.0N/2.54 cm; and/or (ii) an adhesive strength after four days of 1.5N/2.54cm, or 2.0N/2.54cm to 6.3N/2.54cm, or 7.0N/2.54 cm; and/or (iii) an adhesive strength after seven days of 2.0N/2.54cm, or 2.5N/2.54cm, or 5.0N/2.54cm to 6.0N/2.54cm, or 8.0N/2.54 cm; and/or (iv) a bond strength after fourteen days of 2.5N/2.54cm, or 3.0N/2.54cm to 6.0N/2.54cm, or 8.0N/2.54 cm; and/or (v) a bond strength after in-bag boiling test of 0.5N/2.54cm, or 0.80N/2.54cm to 2.2N/2.54cm, or 5.0N/2.54 cm; or 0.50N/2.54cm to 5.0N/2.54 cm; and/or (vi) an adhesive strength after chemical aging of 0.5N/2.54cm, or 0.80N/2.54cm to 2.0N/2.54cm, or 5.0N/2.54 cm; or 0.5N/2.54cm to 5.0N/2.54 cm. In another embodiment, the laminate has one, some or all of the following properties after curing at 45 ℃: (i) the adhesive strength after one day is 6.0N/2.54cm, or 6.4N/2.54cm to 8.5N/2.54cm, or 10.0N/2.54 cm; and/or (ii) an adhesive strength of 5.5N/2.54cm, or 5.8N/2.54cm to 11.0N/2.54cm, or 13.0N/2.54cm after seven days; and/or (iii) a bond strength after fourteen days of 5.0N/2.54cm, or 5.50N/2.54cm to 8.0N/2.54cm, or 12.0N/2.54 cm; and/or (iv) a bond strength after in-bag boiling test of from 1.0N/2.54cm to 5.0N/2.54cm, or 8.0N/2.54 cm; and/or (v) an adhesive strength after chemical ageing of from 0.5N/2.54cm, or from 0.8N/2.54cm to 1.1N/2.54cm, or 5.0N/2.54 cm; or 0.5N/2.54cm to 5.0N/2.54cm, or 0.5N/2.54cm to 1.5N/2.54 cm.

In one embodiment, the first substrate is a monolayer film having a monolayer that is PET and the second substrate is a monolayer film having a monolayer that is an ethylene-based polymer (such as LDPE). In another embodiment, the laminate has one, some or all of the following properties after curing at 25 ℃: (i) the bond strength after two days is 1.0N/2.54cm, or 1.2N/2.54cm to 9.2N/2.54cm, or 10.0N/2.54 cm; and/or (ii) an adhesive strength after four days of 4.0N/2.54cm, or 4.2N/2.54cm to 12.2N/2.54cm, or 15.0N/2.54 cm; and/or (iii) an adhesive strength after seven days of 6.0N/2.54cm, or 10.0N/2.54cm to 12.5N/2.54cm, or 15.0N/2.54 cm; and/or (iv) a bond strength after fourteen days of 6.0N/2.54cm, or 10.0N/2.54cm to 14.2N/2.54cm, or 17.0N/2.54 cm; and/or (v) a bond strength after in-bag boiling test of 3.0N/2.54cm, or 3.5N/2.54cm, or 4.0N/2.54cm to 4.6N/2.54cm, or 10.0N/2.54 cm; or 3.0N/2.54cm to 10.0N/2.54 cm; or 4.0N/2.54cm to 10.0N/2.54 cm; and/or (vi) an adhesive strength after chemical aging of 2.5N/2.54cm, or 2.9N/2.54cm to 6.0N/2.54cm, or 10.0N/2.54 cm; or 2.5N/2.54cm to 10.0N/2.54 cm. In another embodiment, the laminate has one, some or all of the following properties after curing at 45 ℃: (i) the adhesive strength after one day is from 13.0N/2.54cm to 20.0N/2.54cm, or 30.0N/2.54 cm; and/or (ii) an adhesive strength after seven days of 12.0N/2.54cm, or 13.0N/2.54cm to 19.0N/2.54cm, or 20.0N/2.54 cm; and/or (iii) a bond strength after fourteen days of from 10.0N/2.54cm to 15.0N/2.54cm, or 18.0N/2.54 cm; and/or (iv) a bond strength after in-bag boiling test of 2.0N/2.54cm, or 3.5N/2.54cm, or 4.0N/2.54cm to 9.0N/2.54cm, or 10.0N/2.54 cm; or 2.0N/2.54cm to 10.0N/2.54 cm; or 4.0N/2.54cm to 10.0N/2.54 cm; and/or (v) an adhesive strength after chemical aging of from 2.5N/2.54cm to 5.0N/2.54cm, or 10.0N/2.54 cm.

In one embodiment, the first substrate is a monolayer film having a monolayer that is PET and the second substrate is a monolayer film having a monolayer that is a propylene-based polymer (such as polypropylene or further cast polypropylene). In another embodiment, the laminate has one, some or all of the following properties after curing at 25 ℃: (i) the adhesive strength after two days is from 0.05N/2.54cm to 1.30N/2.54cm, or 2.00N/2.54 cm; and/or (ii) an adhesive strength of 3.0N/2.54cm, or 5.0N/2.54cm to 12.0N/2.54cm, or 20.0N/2.54cm after four days; or 3.0N/2.54cm to 20.0N/2.54 cm; and/or (iii) an adhesive strength after seven days of from 7.0N/2.54cm to 16.0N/2.54cm, or 20.0N/2.54 cm; and/or (iv) a bond strength after fourteen days of from 7.0N/2.54cm to 14.1N/2.54cm, or 18.0N/2.54 cm; and/or (v) a bond strength after in-bag boiling test of 3.5N/2.54cm, or 4.0N/2.54cm, or 4.3N/2.54cm to 6.0N/2.54cm, or 10.0N/2.54 cm; or 3.5N/2.54cm to 10.0N/2.54 cm; and/or (vi) an adhesive strength after chemical aging of 6.0N/2.54cm, or 7.9N/2.54cm to 10.0N/2.54cm, or 15.0N/2.54 cm; or 6.0N/2.54cm to 15.0N/2.54 cm. In another embodiment, the laminate has one, some or all of the following properties after curing at 45 ℃: (i) the adhesive strength after one day is 9.0N/2.54cm to 15.0N/2.54cm, or 20.0N/2.54 cm; and/or (ii) an adhesive strength of 9.0N/2.54cm, or 9.6N/2.54cm to 14.0N/2.54cm, or 20.0N/2.54cm after seven days; and/or (iii) a bond strength after fourteen days of from 10.0N/2.54cm to 18.0N/2.54cm, or 20.0N/2.54 cm; and/or (iv) a bond strength after in-bag boiling test of 3.5N/2.54cm, or 4.0N/2.54cm, or 6.5N/2.54cm, or 8.0N/2.54cm to 9.0N/2.54cm, or 10.0N/2.54 cm; or 3.5N/2.54cm to 10.0N/2.54 cm; and/or (v) an adhesive strength after chemical ageing of from 7.0N/2.54cm, or from 7.5N/2.54cm to 9.0N/2.54cm, or 15.0N/2.54 cm.

In one embodiment, the laminate comprises a first substrate that is a metal foil film and a second substrate that is a polypropylene film, and the laminate has an adhesive strength after chemical aging of 0.5N/2.54cm to 5.0N/2.54cm, or 0.90N/2.54cm to 5.0N/2.54 cm.

In one embodiment, the laminate comprises a first substrate that is a PET film, and the laminate has an adhesive strength after in-bag boiling testing of 3.5N/2.54cm to 10.0N/2.54cm, or 4.0N/2.54cm to 10.0N/2.54 cm.

The laminate may comprise two or more embodiments disclosed herein.

E. Method of forming two-part solventless adhesive composition

The present disclosure also provides a method of forming a two-part solventless adhesive composition. In one embodiment, the method comprises (a) providing a polyol component containing (i) PE-a PC and (ii) optionally PT-PO; (B) providing an NCO component; and (C) reacting the polyol component with the NCO component to form a two-part solventless adhesive composition.

The polyol component, PE-A PC, PT-PO, NCO component, and two-part solvent-free adhesive composition can be any of the corresponding polyol component PE-A PC, PT-PO, NCO component, and two-part solvent-free adhesive compositions disclosed herein.

The method may comprise two or more embodiments disclosed herein.

The present disclosure also provides articles containing the laminate. Non-limiting examples of suitable articles include packages, bags, pouches, drawn cans, and containers.

In one embodiment, the laminate contacts the food. "food" is an edible food product.

By way of example and not limitation, some embodiments of the disclosure will now be described in detail in the following examples.

Examples of the invention

The materials used in the examples are provided in table 1 below.

TABLE 1

DCC ═ dow chemical company PMC ═ PMC Organometallix

A. Preparation of polyester-polycarbonate polyols

Preparation of poly (1, 4-butanediol-carbonate) (BDO-PC): a30 gallon 316L stainless steel vessel with an inside diameter of 20 inches was equipped with internal baffles, a variable speed 12 inch turbine wheel, spray rings, hybrid DOWERREM with independent heat and cold circuits^TMClosed loop system of the system and 24 inch packed column. 67958.0 grams (g) BDO was added to the reactor and heated to 150 ℃ with N₂Purge to inertize the reactor and remove water present in the BDO. Adding TYZOR^TMT-PT catalyst (21.6g), and the line previously purged from the reactor was flushed with 600.0g BDO. DMC (102864.0g) was added from a weigh pan using a flow meter and control valve over a period of 6 to 8 hours while maintaining the temperature in the column at 65 ℃. After the DMC addition was complete, the temperature was raised to 195 ℃ and the OH number and used for end group analysis ¹H-NMR was used to follow the progress of the reaction. After 8 hours at 195 ℃ the OH number was found to be 30.7 and¹H-NMR found 25% carbonate end groups. The temperature was reduced to 150 ℃, and 4.1 pounds (lbs) of BDO was added to the reaction. The temperature was brought to 195 ℃ and after 8 hours it was found that the OH number was 54mg KOH/g and the carbonate end groups were less than 1%. A poly (1, 4-butanediol-carbonate) (BDO-PC) was prepared with an OH number of 54mg KOH/g and an Mn of 1960 g/mol.

Preparation of polyester-amide polycarbonate polyol (PE-A PC): the polyester-polycarbonate polyols were synthesized according to the following general procedure, with the detailed formulation composition for each sample provided in table 2. The reaction was run in a glass reactor having a 1000mL three-necked flask equipped with a thermocouple inlet port. One neck of the reactor contains an air inlet adapter, which isComprising 29/42 necks connected by plugs. Feeding the gas inlet with N regulated by an adjustable flow meter₂. The second neck of the reactor contains a custom made mechanical stirring shaft adapter modified to allow vacuum use. The third neck of the reactor contained an offset adapter connected to a 12 inch long column leading to the distillation head and a condenser with a three-neck bottom draw collection flask at the bottom of the condenser. The collection flask had access to J-KEM ^TMOne line to the vacuum regulator and lead to N₂The other line of the bubbler. The 12 inch post offset from the offset adapter was filled with a 5mm glass bead. The column was heated by a heating belt controlled by a set transformer and the column surface temperature was monitored with a thermocouple. Reactor heating was supplied by a heating jacket fed by a control box with an over-temperature cutter. Mechanical agitation was achieved using a custom made 1/4 inch stainless steel paddle and shaft. The reactor was charged with HDO, NPG, PDO and amine monomer. The mixture was degassed under vacuum and subjected to N₂Purged up to three times and then slowly heated to below 100 ℃. Adipic acid (or adipic acid and isophthalic acid) is added and the mixture is allowed to stir for about one hour. The temperature was then raised to 150 ℃ and titanium isopropoxide (supplied by aldrich) was injected. As the distillate started to slow down, the reaction temperature was gradually increased to 210 ℃. Moderate vacuum pressure was applied to drive the reaction to completion. The acid number was monitored to determine the end point of the reaction. When the acid value is less than 1.0, the polyester component is considered intact. BDO-PC and HDO (equimolar to BDO-PC) prepared as described above were then added to the polyester component at room temperature and the solution was heated to 210 ℃ for four hours.

TABLE 2

¹Weight (%) of charged monomer, NM-not measured based on the total amount of charged monomer²The acid number and OH number are measured in mg KOH/g.³The viscosity is measured in mPas units.

B. Preparation of phosphate-terminated polyol

A1 liter multi-neck round bottom flask was dried in an oven, purged with dry nitrogen for 30 minutes, and charged with 149.96 grams of VORANOL^TMCP 450 (polyether polyol) and placing in N of 70mL/min₂Under the cleaner. The syringe was loaded with 3.395g of 115% polyphosphoric acid (PPA) (supplied by sigma aldrich). Dropwise addition of PPA to VORANOL^TMIn CP 450 and vigorously agitated. A minimum temperature increase was observed. The reactor contents were heated to 100 ℃ for 1 hour, and then cooled to 45 ℃. 21.65g of ISONATE^TM125M (MDI blend) was slowly added to the reactor. A significant exotherm was controlled by applying an ice bath to keep the reaction kettle below 75 ℃. A yellow to amber development was observed. The reactor was then maintained at 65 ℃ for 1 hour, at which time the contents were cooled and packaged. The phosphate-capped polyol (PT-PO) prepared did not contain excess or free MDI. PT-PO has a solids content of 100% by weight, an OH number of 270mg KOH/g, an acid number of 24.0mg KOH/g, a viscosity of 17,820 mPas at 25 ℃, an Mn of 780g/mol, an Mw of 1415g/mol, an Mz of 2325g/mol and an Mw/Mn of 1.82. PT-PO contains 26.0 wt.% species with Mw less than 500g/mol, and 41.3 wt.% species with Mw less than 1000 g/mol.

C. Preparation of polyol component

PE-a PC 1-10 and polyester 11 prepared as described above were mixed with PT-PO to form a sample polyol component. The composition and characteristics of each sample polyol component are provided in table 3. In the table, "CS" refers to a comparative sample.

D. Preparation of two-component solvent-free adhesive composition

Two-component solventless adhesive composition is prepared by mixing (A) MOR-FREE^TMC-33 (aliphatic isocyanate prepolymer) was prepared with (B) one of the example polyol component (Ex PC)1-4 or 8-13, the comparative sample polyol component (CS PC)5-7, MOR-FREE L82-105, or MOR-FREE 1390A mixed in a kettle at room temperature (23 ℃) until a homogeneous mixture was obtained, forming a two part solventless adhesive composition. The components of each of the example and comparative example adhesive compositions are provided in tables 4 and 5.

TABLE 3

The wt.% in Table 3 are based on the total weight of the corresponding Polyol Component (PC)

E. Forming a laminate

A Low Density Polyethylene (LDPE) film containing a slip agent is provided as a monolayer film having a thickness of 1.5 mils (GF-19 available from Berry Plastics Corp.).

A cast polypropylene film is provided which is a single layer film having a thickness of 3 mils.

Poly (ethylene glycol-terephthalate) (PET) film is provided as a monolayer film (92LBT, available from DuPont) having a thickness of 1 mil (24.5 μm).

A metal foil film (aluminum foil) is provided. The metal foil film was a single layer film having a thickness of 1.5 mils (38.1 μm). Based on the coating weight of 3.26g/m²(2.00 lbs/ream) ADCOTE was used^TM577 coreactant F (solvent-based 2-component polyurethane adhesive, commercially available from the dow chemical company) pre-laminates a metal foil film with a PET film (12 μm thick, 48 gauge) to form a metal foil pre-laminate (Prelam) having the following structure (I):

PET film/ADCOTE^TM577 co-reactant F adhesive layer/metal foil film structure (I).

The example and comparative example adhesive compositions were loaded into a nordmecanica Labo Combi pilot laminator. The laminator nip temperature was maintained at 60 ℃, the oven temperature was set at 25 ℃ for each zone, and the laminator was operated at a speed of 30 meters per minute.

Applying the adhesive composition to a metal foil pre-laminate (Prelam) or a PET film (92LBT) to form the following structures (II) and (III):

prelam/adhesive composition Structure (II)

PET/ADHESIVE COMPOSITION STRUCTURE (III)

In structure (II), the adhesive composition directly contacts the surface of the metal foil film layer of the metal foil pre-laminate (having structure (I)).

Contacting a LDPE film or a cast polypropylene film with an adhesive layer to form a laminate having structure (IV), structure (V), structure (VI), or structure (VII):

Prelam/adhesive composition/LDPE Structure (IV)

Prelam/adhesive composition/cast polypropylene structure (V)

PET/adhesive composition/LDPE construction (VI)

PET/adhesive composition/cast Polypropylene Structure (VII)

Two samples of each example and comparative example laminate were formed. One sample was cured at 25 ℃ and 50% relative humidity as shown in table 4. Another sample was cured in an isothermal oven at 45 ℃ at 30% relative humidity as shown in table 5. The properties of each laminate example and comparative sample are provided in tables 4 and 5. In tables 4 and 5, "FS" indicates film tensile Failure Mode (FM); "FT" indicates film tear or disruption FM; "DL" indicates hierarchical FM; "AT" indicates adhesive transfer FM, where the adhesive is transferred to a second film; "AS" indicates cohesive failure or adhesive separation FM, where adhesive is present on both films; "CDL" indicates complete delamination, where bond strength is not measurable; and the "NM" indicates that no measurement is made.

F. Results

As shown in Table 4, CS 10-11 each included an adhesive layer formed from (A) an NCO component (MOR-FREE C-33) and (B) a polyol component lacking PE-A PC (MOR-FREE L82-105 and CS PC 5, respectively). The laminate structures of CS 10 and CS 11 having structures (VI) and (VI) (i.e., containing PET film) and cured at 25 ℃ and 50% Relative Humidity (RH) each exhibited an adhesive strength of less than 3.5N/2.54cm after the in-bag boiling test. Thus, CS 10 and CS 11 each exhibited insufficient adhesive strength after the in-bag boiling test.

As shown in Table 4, each of Ex 1-9 included an adhesive layer formed from (A) an NCO component (MOR-FREE C-33) and (B) a PE-A PC-containing polyol component (PC 1, PC 3, PC 4, PC 8, PC 9, PC 10, PC 11, PC 12, and PC 13, respectively). The laminated structures of Ex 1-9 with structures (VI) and (VI) (i.e., containing PET film) and cured at 25 ℃ and 50% RH each exhibited an adhesive strength of greater than 3.5N/2.54cm after the in-bag boiling test. Thus, Ex 1-9 each exhibited sufficient adhesive strength after the in-bag boiling test.

TABLE 4.25 ℃ curing temperature

TABLE 5.45 ℃ curing temperature

As shown in Table 5, CS 14-16 each included an adhesive layer formed from (A) an NCO component (MOR-FREE C-33) and (B) a polyol component lacking PE-A PC (MOR-FREE 1390A, CS PC 6, and CS PC 7, respectively). The laminated structures of CS 14-16 with structure (V) (i.e., Prelam/adhesive composition/cast polypropylene) and cured in an isothermal oven at 30% RH at 45 ℃ each exhibited an adhesive strength of less than 0.5N/2.54cm after chemical aging. Thus, CS 14-16 each exhibited insufficient adhesive strength after chemical aging.

As shown in Table 5, Ex 12-13 each included an adhesive layer formed from (A) an NCO component (MOR-FREE C-33) and (B) a PE-A PC-containing polyol component (PC 2 and PC 3, respectively). Ex 12-13 laminates with structure (V) (i.e., Prelam/adhesive composition/cast polypropylene) and cured in an isothermal oven at 30% RH at 45 ℃ each exhibited an adhesive strength greater than 0.50N/2.54cm after chemical aging. Thus, Ex 12-13 each exhibited sufficient adhesive strength after chemical aging.

It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.