Adhesive composition

Abstract

To provide a two component solventless polyurethane-based laminating adhesive composition suitable for use in a one shot laminating process / apparatus.SOLUTION: A two component solventless laminating adhesive composition comprising: (A) at least one isocyanate component comprising at least one isocyanate; and (B) at least one polyol component comprising: (Bi) at least one amine-initiated polyol; (Bii) at least one aliphatic polyester polyol; and (Biii) at least one polyether polyol, A two component solventless laminating adhesive composition wherein (Bi) has a chemical structure of structure (I): wherein R1, R2 and R3 are each independently a C1-C6 linear or branched alkyl group; wherein R1, R2 and R3 each independently optionally further comprise an ether group and a hydroxyl group; and wherein R1, R2 and R3 each independently optionally comprise a tertiary amine or a secondary amine.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component solventless polyurethane laminating adhesive composition and a two-component solventless polyurethane laminating adhesive composition. The present invention relates to laminates made using a methacrylate-based laminating adhesive composition. [Background technology]

[0002] The adhesive composition is useful for a wide variety of purposes. For example, the adhesive composition may be made of polyethylene terephthalate. Polypropylene, polyester, polyamide, metal, metallized, paper, or cellophane and other substrates together to form composite films, i.e., laminates. The use of adhesives in different end use applications is generally known. For example, adhesives is a manufacturer of films / films and fillers used in the packaging industry, especially for food packaging. It can be used in the production of rubber / foil laminates. Laminating adhesives generally fall into three categories: solvent-based, water-based, and solvent-free. The performance of adhesives varies depending on the category and the application to which the adhesive is applied. Bad.

[0003] Solventless laminating adhesives are up to 100% solvent-free without the use of either organic solvents or aqueous carriers. The solid content of the adhesive can be applied. When applying, the organic solvent or water must be dried from the adhesive. Because no adhesive is required, these adhesives can be run at high line speeds and are ideal for rapid bonding. Solvent-based and water-based laminating adhesives are preferred in applications requiring adhesive application. The rate at which the solvent or water can subsequently be effectively dried and removed from the laminate structure is limited. For environmental, health, and safety reasons, the laminating adhesive is preferably water-based or solvent-free. It is a drug.

[0004] There are many types within the category of solventless laminating adhesives. One particular type is premixed Two-component polyurethane laminating adhesives are typically used. Polyisocyanate-based laminating adhesives contain isocyanate-containing prepolymers and / or polyisocyanates. and a second component comprising a polyol. Excess isocyanate and polyether containing two or more hydroxyl groups per molecule It can be obtained by reaction with polyol and / or polyester polyol. The component is a polyether polyol that starts with two or more hydroxyl groups per molecule. and / or polyester polyol. The two components are combined in a predetermined ratio. , or "premixed," and then applied to a first substrate (a "carrier web"). The first substrate is then combined with a second substrate to form a laminate structure.

[0005] Additional substrate layers are added to the structure, with additional layers of adhesive composition disposed between each successive substrate. The adhesive can then be cured either at room temperature or at an elevated temperature, thereby The substrates are bonded together.

[0006] Further processing of the laminated structure depends on the cure rate of the adhesive. The mechanical bond between the bonded substrates is sufficient to allow further processing, making lamination processing applicable. Cure speed is indicated by the time it takes to comply with applicable regulations (e.g., food contact regulations). Slow conversion efficiency is reduced. Premixed two-component solventless laminating adhesives are superior to conventional solvent-based adhesives. They exhibit weaker initial bonds and slower cure rates compared to adhesives containing adhesives containing acrylic acid. The general trend is towards faster curing laminating adhesives. Specifically, by quickly moving finished products from the warehouse, Increased production capacity and flexibility to process new orders (e.g., retail promotional campaigns) To improve operational efficiency, a compound with much higher reactivity than existing adhesive compositions was developed. However, the adhesive composition used to form the laminate is The composition, when used in a laminate structure including a metal substrate and / or a metallized substrate, At relatively high line speeds (e.g., speeds exceeding 250 meters per minute [m / min]), At this temperature, defects can be visually observed in the resulting laminate. This is due to poor wetting and air entrapment during the process.

[0007] Therefore, improved bond strength, faster cure rates, and bonding to metal substrates and / or metal Two-component solventless polyurethane laminating adhesive compositions with enhanced adhesion to laminate substrates Things are desirable.

[0008] Additionally, the two components of the adhesive formulation are premixed, as is done using conventional laminating equipment. and the entire adhesive formulation mixture is applied to the carrier web prior to contacting the carrier web with the second substrate. It would be desirable to provide an adhesive formulation that is prepared without the need for coating on a rear web. To avoid premixing, for example, apply the first adhesive component onto the surface of the first film. and applying a second adhesive component (separate from the first adhesive component) onto the surface of the second film. By doing so, the two adhesive components are separated into two separate fillers. It is known to apply a first adhesive component to a film substrate to hold the two substrates together. 2 adhesive component, so when the two components on the two films come into contact with each other The two reactants bond together by reacting to bond the two films together via the reacted adhesive compound. The resulting mixture forms a reactive adhesive compound that bonds to the adhesive.

[0009] Generally, a "one shot" lamination method is used, which utilizes a specific lamination device (e.g., a one shot laminator). Using a "shot lamination" process, two films containing two separate components of the adhesive formulation are bonded together. The process of laminating the films together to form a laminate is typically performed using a one-shot laminator. operates at high line speeds (e.g., 200 m / min or more) to carry out the coating process However, previously known two-component solventless polyurethane laminating adhesive compositions Disadvantages of using in a one-shot lamination process / equipment include, for example, poor metal adhesion. Poor chemical resistance / productivity, short pot life, and poor stability due to phase separation Examples include:

[0010] Therefore, the above-mentioned drawbacks, limitations, and deficiencies of previously known solvent-free adhesive formulations To produce multi-layer laminates that overcome the It is therefore desirable to provide a two-component, solvent-free polyurethane-based laminating adhesive composition suitable for . Summary of the Invention

[0011] One embodiment of the present invention is a two-component solventless laminating adhesive composition comprising: (A) at least At least one isocyanate component containing one isocyanate and (B)(Bi) (Bii) at least one amine-initiated polyol; (Bii) at least one aliphatic polyester; polyol; and (Biii) at least one polyether polyol. and one polyol component.

[0012] Another embodiment of the present invention relates to a process for preparing the above solventless laminating adhesive composition.

[0013] In yet another embodiment of the present invention, a laminate is produced using the solventless laminating adhesive composition described above. and a manufacturing process for the laminated structure. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the adhesives art, two-part (i.e., two-component) adhesive systems or adhesive compositions are a first reactant (or first portion) comprising a thiocyanate component (herein "component A"); a second reactant (or second portion) comprising a polyol component (herein "Component B"); By combining or mixing Component A and Component B, a two-part reaction mixture is formed. In one broad embodiment, the present invention provides a method for preparing an adhesive composition comprising: It contains component A, which is a cyanate component, and component B, which is at least one polyol component. A two-component solventless laminating adhesive composition (referred to herein as "SLAC") for producing laminates. (abbreviated)

[0015] The SLACs of the present invention are particularly suitable for use in laminate structures containing metal or metallized substrates. SLAC, when used in laminate structures containing metal and / or metallized substrates, offers a Component: Faster curing speed compared to solvent-free adhesive compositions. SLAC is highly reactive and cures quickly. Due to its fast rate, SLAC is ideally suited for use with typical existing adhesive application equipment. This is because the two components react very quickly, causing the adhesive to gel and become sticky when applied to the substrate. For this reason, SLAC is not suitable for use in processes typically performed in the prior art. The isocyanate and polyol components are premixed and coated onto a carrier web as shown. It is formulated to be applied separately onto two different substrates rather than spread across one another.

[0016] In particular, SLAC involves uniformly applying component A, an isocyanate component, to the surface of a first substrate. and component B, a polyol component, can be applied to the surface of the second substrate. The surface of the first substrate is then brought into contact with the surface of the second substrate to bond the two together. The components of the adhesive composition are mixed and reacted to form the laminate. is curable.

[0017] Isocyanate component Component A, which is the isocyanate component (NCO component) of the present invention, can be, for example, isocyanate. isocyanate monomer, isocyanate prepolymer, polyisocyanate, or a mixture thereof Conventional isocyanates known in the art for forming polyurethane adhesive compositions containing Examples of the polyisocyanate include aliphatic polyisocyanates. Isocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, isocyanates Examples of the polymers include prepolymers, and combinations of two or more thereof. When used, "polyisocyanate" means any polyisocyanate containing two or more isocyanate groups. "Aliphatic polyisocyanates" are polyisocyanates that do not contain any aromatic rings. "Alicyclic polyisocyanates" are aliphatic polyisocyanates whose chemical chains have a cyclic structure. "Aromatic polyisocyanates" are a subset of polyisocyanates. It is a polyisocyanate containing an aromatic ring.

[0018] Examples of suitable aliphatic and cycloaliphatic polyisocyanates useful in the present invention include: Examples include, but are not limited to, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isocyanate, ethyl cyclohexane diisocyanate, propyl cyclohexane diisocyanate Cyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate butane diisocyanate, pentane diisocyanate, hexane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanates, such as 4-isocyanatomethyl-1,8-octane diisocyanate Decane di- and triisocyanate (TIN), undecane di- and triisocyanate nate, and dodecane di- and triisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diisocyanatodicyclohexyl Lumetane (H 12 MDI), 2-methylpentane diisocyanate (MPDI), 2,2 ,4-Trimethylhexamethylene diisocyanate / and 2,4,4-trimethylhexa Methylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), Xylylene diisocyanate (XDI), 1,4- or 1,3-bis(isocyanatomethyl) cyclohexane (H6XDI), tetramethylxylylene diisocyanate, and Examples of suitable hydroxyl groups useful in the present invention include dimers, trimers, and derivative mixtures of two or more of these hydroxyl groups. Examples of aliphatic polyisocyanates and alicyclic polyisocyanates include XDI polyisocyanates. Reisocyanate, H6XDI polyisocyanate, XDI isocyanurate, HDI Polyisocyanate, H 12 MDI-based polyisocyanate, IPDI-based polyisocyanate Also included are esters, and mixtures of two or more thereof.

[0019] In one preferred embodiment, the aliphatic isocyanate component useful in the present invention includes, for example, , XDI-based polyisocyanates, HDI-based polyisocyanates, and mixtures thereof. can be done.

[0020] Some examples of commercially available aliphatic isocyanate components useful in the present invention include, for example: Desmodur® available from The Covestro Company ) N3200 and Desmodur® N3300, and mixtures thereof. can be done.

[0021] Aromatic isocyanate components useful as component A in the present invention include, for example, 1, 3- and 1,4-phenylene diisocyanate; 1,5-naphthylene diisocyanate, 2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate 2,4'-TDI, 2,4'-diphenylmethane diisocyanate (2,4'-M DI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 3,3' -Dimethyl-4,4'-biphenyl diisocyanate (TODI) and its isomers; Poly 1. Polyisocyanates, including but not limited to 1. 2 ... At least one polyisocyanate compound can be mentioned.

[0022] Some examples of commercially available aromatic isocyanate components useful in the present invention include, for example, T ISONATE (trademark) available from The Dow Chemical Company ) 125M, ISONATE™ 50OP, and ISONATE™ 143L; DESMODUR® available from The Covestro Company ) E 2200 / 76, and mixtures thereof. One advantageous property of the cyanate component is that it can cure quickly. An adhesive may be provided.

[0023] Also suitable isocyanate compounds for use as component A according to the present disclosure include, for example: For example, isocyanate prepolymers can be mentioned. In one embodiment, it is greater than 2.0 (>), in another embodiment, it is 3.0 to 10.0, and in yet another embodiment, it is In terms of form, (a) polyisocyanate compounds with a stoichiometric ratio (NCO / OH) of 4.0 to 7.0 (b) a reaction product of the polyol component and (c) a polyol component.

[0024] Polyisocyanates, component (a) may be, for example, the aromatic polyisocyanates mentioned above, fatty and the polyisocyanate is selected from aromatic polyisocyanates, alicyclic polyisocyanates, and mixtures thereof. It reacts with polyisocyanates to produce isocyanates, also known as "polyurethane prepolymers." Component (b), a suitable polyol component capable of forming an anate prepolymer. Examples of the compounds include compounds having a hydroxyl group, an amino group, and a thio group. The polyisocyanate component is used to form the isocyanate prepolymer useful in the present invention. Examples of polyol components that can react with the Polyester polyol, polycaprolactone polyol, polyacrylate, polycarbonate Natural oil-based polyols, ester polyols, natural oil-based polyols, and mixtures of two or more thereof.

[0025] React with a polyisocyanate to form an isocyanate prepolymer useful in the present invention. The compatible polyol component also depends on the hydroxyl number and hydroxyl value of the isocyanate-reactive component. They can be characterized by their hydroxyl group functionality, also known as "hydroxyl number," "OH#," or "Hydroxyl value" is a measure of the content of free hydroxyl groups in a chemical substance. The hydroxyl value is the number of hydroxyl groups that can be obtained by acetylating one gram of a chemical that contains free hydroxyl groups. is the number of milligrams of potassium hydroxide (KOH) required to neutralize the added acetic acid. The hydroxide number (OHN) is usually expressed as milligrams of potassium hydroxide per gram of chemical. The hydroxyl number is expressed as (mg KOH / g). It is decided.

[0026] "Hydroxyl group functionality" is the number of hydroxyl groups present in one molecule of a compound Hydroxyl functionality was measured according to ASTM D4274-16, and the results were In some embodiments, it is reported as an integer greater than or equal to 1, and in other embodiments, it is reported as an integer between 1 and 6. In this form, the average hydroxyl group functionality of the polyol component is, for example, 1 in one embodiment. 0 to 6.0, in another embodiment 1.8 to 4.0, and in yet another embodiment 2.0 to 3.0. could be.

[0027] The compound having an isocyanate group, such as component A of the present invention, is It can also be characterized by the weight percentage of isocyanate groups (NCO) present. The weight percentage of isocyanate groups is referred to as "NCO%" and is specified in ASTM D257 2-97. For example, the NCO content of component A is, in one embodiment, 7% or more. in other embodiments, it is 10% or more. In yet another embodiment, the N The CO content is not more than 30%, and in yet another embodiment not more than 25%.

[0028] Additional isocyanate-containing compounds suitable for use in accordance with the present invention include 4-methyl- Cyclohexane 1,3-diisocyanate; 2-butyl-2-ethylpentamethylene diisocyanate Cyanate;3(4)-Isocyanatomethyl-1-methylcyclohexyl isocyanate ;2-Isocyanatopropylcyclohexylisocyanate;2,4'-Methylenebis( Cyclohexyl)diisocyanate; 1,4-diisocyanato-4-methyl-pentane, and mixtures of two or more thereof, but are not limited to these.

[0029] In some embodiments, one or more of the above isocyanate compounds are added in a predetermined amount to Component A. It can be added to component A, or to component B, or to both component A and component B.

[0030] Polyol component In the present invention, component B comprises (Bi) at least one amine-initiated polyol; (Bi i) at least one aliphatic polyester polyol; and (Biii) at least one and optionally other optional components or additives. The polyol component includes a mixture or blend. The concentrations of (Bi) to (Biii) are A laminate that can be processed in a one-shot lamination process and has a good adhesive appearance, i.e. That is, bubbles and orange peeling at high lamination line speeds (e.g., over 200 m / min) The adhesive strength is sufficiently high to produce an adhesive composition capable of producing a defect-free laminate of the present invention. Other advantages of LAC over previously known solvent-free adhesive systems include: These include (1) good adhesive properties and (2) fast curing properties. The laminate has good heat resistance and chemical resistance, which are properties that are preferably imparted to packaging products made from the laminate. It is useful in a one-shot lamination process to fabricate suitable multi-layer laminates.

[0031] By including an amine-initiated polyol in the polyol component, existing two-component solventless Provides higher reactivity and faster cure than traditional polyols used in adhesive compositions Amine-initiated polyols contain primary hydroxyl groups and at least one tertiary amine. In some embodiments, the polyol component comprises a non-amine-initiated polyol. Each polyol type may comprise one or more polyols. Alternatively, each polyol type may be a different type of polyol. In some embodiments, one polyol type may comprise a mixture of one or more polyols. The other polyol type may be a mixture of different types of polyols. may be.

[0032] Amine-initiated polyols contain primary hydroxyl groups and at least one tertiary amine. Amine-initiated polyols suitable for use in accordance with the present invention include a backbone incorporating one or more amines. prepared by alkoxylating an amine initiator with one or more alkylene oxides. do.

[0033] In some embodiments, the amine-initiated polyol has the chemical structure of structure (I):

[0034] [ka] (In the formula, R 1 , R 2 and R 3 are each independently an organic group. may each independently be a C1 to C6 linear or branched alkyl group, and may contain ether groups and hydroxyl groups, each independently a tertiary amine and and secondary amines.

[0035] The amine-initiated polyol may be from 2 to 12 in one embodiment, from 3 to 10 in another embodiment, or In another embodiment, it contains a functionality of 4 to 8. "Isocyanate titer" refers to the number of isocyanate reactive sites per molecule. In one embodiment, the number of the molecules is 5 to 1,830, in another embodiment, 20 to 100, and in yet another embodiment, In the form of hydroxyl number of 31 to 40. When used in reference to the polyol component, The "hydroxyl number" is a measure of the amount of reactive hydroxyl groups available to react. The number is determined by wet analysis and is the number of hydroxyl groups found in 1 gram of sample. It is reported as milligrams of potassium chloride. The commonly used method is described in ASTM D4274D. The oar has a viscosity at 25 degrees Celsius (°C) of 500 millipascal seconds (mPa) in one embodiment. -s) to 20,000 mPa-s, in another embodiment 1,000 mPa-s to 15,00 0 mPa-s, and in yet another embodiment, 1,500 mPa-s to 10,000 mPa-s. be.

[0036] The amount of amine-initiated polyol in the polyol component is determined by the weight of the polyol component, component B (all That is, by weight based on the total weight of the polyol component, in one embodiment at least twice as much %, in another embodiment at least 4% by weight, and in yet another embodiment at least 6% by weight The amount of at least one amine-initiated polyol in the adhesive composition is In one embodiment, the weight of the polyol component in component B is In some embodiments, it does not exceed 60% by weight, in other embodiments it does not exceed 50% by weight, and in still other embodiments it does not exceed 60% by weight. does not exceed 40% by weight.

[0037] The aliphatic polyester polyol compounds, component (Bii), useful in the SLAC of the present invention are For example, polyester polyols derived from aliphatic polycarboxylic acids and polyols In one embodiment, for use in the polyol co-reactant component (Component B), Suitable polyester polyol compounds may, for example, have a number average molecular weight of 4,000 g / mol or less. Molecular mass (M n ) can be selected from polyester polyols having the following structure. The polyester polyol has an OH functionality of 1.8 or more and 3 or less (i.e., 1.8≦f≦3). value (f) and an OH value of 30 mg KOH / g to 200 mg KOH / g As used herein, "OH number" or "OH#" refers to the number of OH atoms in one gram of polyol. It is characterized by the milligrams of potassium hydroxide equivalent to the hydroxyl content.

[0038] In another embodiment, polyester polyol compounds suitable for use in SLAC include For example, polycondensates of diols, and optionally polyols (e.g., triols, tetraols, etc.). traol), and mixtures thereof, and aliphatic dicarboxylic acids, and mixtures thereof In another embodiment, the polyester polyol compound may be an aliphatic diol. Derived from carboxylic acids, their corresponding anhydrides, or the corresponding esters of lower alcohols You can also do this.

[0039] Suitable diols useful in the present invention include ethylene glycol; butylene glycol; Diethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,3 -Butanediol; 1,4-Butanediol; 1,6-Hexanediol; 2-Methyl- 1,3-propanediol; neopentyl glycol, and mixtures thereof. In one embodiment, polyesters having an OH functionality of >2 are used. To achieve a terpolyol, a polyol having an OH functionality of 3 or >3 may be optionally Optionally, an adhesive composition (e.g., trimethylolpropane, glycerol, erythritol) The sugars may be included in the sugars (e.g., ethanol, or pentaerythritol).

[0040] Suitable aliphatic dicarboxylic acids useful in the present invention include cyclohexanedicarboxylic acid, ... Dipic acid, azelaic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, itaconic acid , malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2- Examples include dimethyl succinic acid, trimellitic acid, and mixtures thereof. The anhydrides of such acids may also be used. Monocarboxylic acids such as xanthic acid should be minimized or should be used in the compositions of the present invention. should be excluded from the

[0041] The aliphatic polyester polyol compound in component B, which is a polyol component, The amount of i) is typically 5% by weight, in one embodiment, based on component B, the polyol component. in another embodiment, from 8% to 40% by weight, based on the polyol component, component B; % by weight; in yet another embodiment, it can be 10% to 30% by weight.

[0042] Generally, M of a polyester polyol compound n is greater than 400 g / mol in one embodiment In another embodiment, greater than 500 g / mol, and in yet another embodiment, greater than 600 g / mol, and In another embodiment, it may be greater than 800 g / mol. M of the mol compound n In one embodiment, it is less than 3,000 g / mol, and in another embodiment, it is less than 2, in yet another embodiment, it can be less than 2,000 g / mol. Cut.

[0043] Component (Biii), the polyether polyol component useful in the present invention, includes, for example, For example, polypropylene glycol, polytetramethylene ether glycol, polybutylene oxide-based polyols, copolymers thereof, and mixtures thereof, Generally, the polyether polyol may be 1,500 in one embodiment. in another embodiment less than 1,000 g / mol, and in yet another embodiment less than 5 M from 0 g / mol to 1,500 g / mol n In another embodiment, the polyether Polyols have an M of 150 g / mol to 1,500 g / mol. n and 2.0 to 6.0 officials It has value.

[0044] Examples of suitable polypropylene glycols useful in the present invention include, for example, propylene glycol oxides, ethylene oxide-based polyols, or propylene glycol; Dipropylene glycol, sorbitol, sucrose, glycerin, and / or their The initiator may be a mixture of, but is not limited to, a mixture of, for example, , and polypropylene glycol, The Dow Chemical Company VORANOL™ available from NY; PLURACO available from BASF L™; POLY-G™, POLY-L™ available from Lonza; and POLY-Q™; and ACCLAIM™ available from Covestro ); and mixtures thereof. In a preferred embodiment, the and M of 150 g / mol to 1,500 g / mol n Polypropylene having Glycol is used.

[0045] Examples of suitable polytetramethylene ether glycols useful in the present invention include, e.g. For example, POLYTHF™ available from BASF Company; Invista TERTHANE™ available from Epson; PTM available from Mitsubishi G™; and PTG™ available from Dairen; and mixtures thereof. In a preferred embodiment, functionalities of 2 to 6 and 2 M from 50g / mol to 1,500g / mol n Polytetramethylene ether glycol having Calls are used.

[0046] Examples of suitable polybutylene oxide-based polyols useful in the present invention include, for example, polybutylene oxide-based polyols such as Butylene oxide homopolymer polyol, polybutylene oxide-polypropylene oxide copolymer polyols, and polybutylene oxide-polyethylene oxide copolymers and mixtures thereof. In one embodiment, the functionality is from 2.0 to 6.0 and the molecular weight is from 150 g / mol to 1,500 g / mol A polybutylene oxide-based polyol having an Mn of

[0047] In other embodiments, polyether polyols useful in the present invention include, for example, ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol , Trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol, trimethylolpropane, triisopropanolamine, neopen and mixtures thereof, such as low molecular weight glycols, Includes, but is not limited to, recalls.

[0048] Generally, the amount of polyether polyol, component (Biii), used in the present invention is: In one embodiment, 20% by weight to 80% by weight of the total components in component B, which is the polyol component, % by weight, in another embodiment 30% by weight to 70% by weight, in yet another embodiment 40% by weight to It is 60% by weight.

[0049] In some embodiments, in addition to components (Bi) through (Biii), any number of other different The polyol may be included in the adhesive composition, for example, in the polyol component. Examples of polyols other than (Bi) to (Biii) include non-amine-initiated polyols. Other polyester polyols, other polyether polyols, polycarbonate polyols ol, polyacrylate polyol, polycaprolactone polyol, polyolefin polyols, natural oil polyols, and combinations of two or more thereof. In some embodiments, other polyols, if used, include but are not limited to: A When measured by the method of STMD2196, the viscosity at 25°C is, for example, In one embodiment, the viscosity is 30 mPa-s to 40,000 mPa-s, and in another embodiment, the viscosity is 50 mPa-s to 3 0,000 mPa-s, and in yet another embodiment, 70 mPa-s to 20,000 mPa-s In a preferred embodiment, the other polyol, if used, is 100mPa-s to 10,000mPa-s at 25°C when measured by method 96 It has a viscosity of s.

[0050] The amount of other polyols in the adhesive composition, if used, is in one embodiment at least 0% by weight, in another embodiment at least 5% by weight, and in yet another embodiment at least 10% by weight The amount of other polyols in the adhesive composition, if used, is in weight percent. In one embodiment, the amount does not exceed 40% by weight, based on the total amount of components in component B, and in another embodiment, In some embodiments, it does not exceed 30% by weight, and in yet other embodiments, it does not exceed 20% by weight.

[0051] In some embodiments, one or more of the above polyol compounds are added in a predetermined amount to the component A. It can be added to component A, to component B, or to both component A and component B.

[0052] In some embodiments, additives can be included in the SLAC of the present invention. Examples of such additives include tackifiers, plasticizers, rheology modifiers, adhesion promoters, antioxidants, etc. Examples of additives include blocking agents, fillers, colorants, surfactants, solvents, and combinations of two or more thereof. Examples include, but are not limited to:

[0053] Adhesive formation In one broad embodiment, the SLAC of the present invention comprises at least one isocyanate compound. Component A, which is at least one polyol component; Component B, which is at least one polyol component; and optionally Generally, the reactive adhesive composition of the present invention is prepared by mixing the following components or additives: The "combining" step of components A and B to form the object is carried out at high line speeds (e.g., 200 m / s). This is done during the one-shot lamination process, which operates for 10 minutes or more. In this example, a process step is used to separate a first film containing component A into a second film containing component B. The first film is then placed in contact with a second film, which is then coated with a polymeric polymer, and the two components (co-reactants) come together to coat the first film. A uniform, homogeneous reactive SLAC is formed that is interposed between the first and second films.

[0054] When the two components (co-reactants) come into contact with each other, a The reactive SLAC intervening between the two is formed. The resulting SLAC is used to prepare a laminate, which is then used to make a laminate article or product. The SLAC containing the CR component of the present invention is laminated using a one-shot lamination process. Some advantageous properties of the laminate include, for example, (1) the "slitting" of the laminate; The "time" is, for example, 2 hours after lamination (which is the time when a typical conventional purpose adhesive is used). (2) The time required for lamination can be shortened to 2-3 days (when lamination is used). The "time to delivery" for the body is, for example, 2 days (when using a typical conventional adhesive) The advantages of this method are that it can be shortened to a time shorter than the usual 5 to 7 days.

[0055] Laminate formation In a broad embodiment, the laminate structure of the present invention comprises at least two film layer substrates, and a combination of two substrates adhered or bonded to one another by an adhesive layer formed between the substrates, The adhesive layer is formed by using the SLAC of the present invention. For example, a laminate structure (a) a first film substrate; (b) a second film substrate; and (c) layers (a) and (b). b) a layer of the SLAC described above for bonding to the substrate; and optionally one or more other optional layers. Any film substrate can be used to prepare the multi-layer laminate structure.

[0056] In the present invention, the laminate structure is formed by bonding two separate components of the adhesive to two separate film substrates. For example, component A is applied to a first film substrate, Component B is applied to the second film substrate. The two film substrates are then combined and the two The parts are brought into contact with each other to form the SLAC.

[0057] The isocyanate and polyol components of SLAC are compounded separately to form a laminate structure. It is contemplated that the data will be stored until it is desired to create a new data set. The socyanate component and polyol component are in a liquid state at 25°C. If necessary, the adhesive composition may be heated to a liquid state. Being decoupled from the curing process, the components can be stored separately indefinitely.

[0058] The laminate containing SLAC is obtained by mixing the isocyanate component and the polyol component of the adhesive composition in two steps. It can be formed by applying the coating separately to different substrates, e.g., two films. As used herein, a "film" is defined as a film having one dimension equal to or greater than 0.5 millimeters ( Any dimension that is 1 centimeter (cm) or less and the other two dimensions are both 1 centimeter (cm) or greater A "polymer film" is a film made from a polymer or a mixture of polymers. The composition of the polymer film is typically 80% of one or more polymers. % by weight or more.

[0059] For example, a layer of an isocyanate component is applied to the surface of a first substrate. In this embodiment, the thickness of the layer of the isocyanate component on the first substrate is 0.5 microns (μm) to 1 A layer of the polyol component is applied to the surface of the second substrate. In an embodiment, the thickness of the layer of the polyol component on the second substrate is 0.5 μm to 1.5 μm. By controlling the thickness of the layer applied to each substrate, the ratio of the components can be controlled. In some embodiments, the isocyanate component and polyol in the final SLAC The mixing ratio of the components is 100:100 in one embodiment, 100:90 in another embodiment, and In another embodiment, it can be 100:80. The SLAC of the present invention is a conventional adhesive. It is more tolerant than the conventional coating, and allows for some coating weight variation (e.g., up to about 10% coating This allows for accurate measurement of the weight of the sample.

[0060] The surfaces of the first substrate and the second substrate are then pressed together by a roller, such as a nip roller. The isocyanate component and the polyol component are passed through a device for applying external pressure to the substrate of 2. When the first and second substrates are bonded together, a curable adhesive mixture layer is formed. When these are combined, the thickness of the curable adhesive mixture layer is 1 μm to 5 μm in one embodiment. The first and second substrates are brought together and the components contact each other, causing the isocyanate component and the polyisocyanate component to bond. The all ingredients begin to mix and react, which marks the beginning of the curing process.

[0061] Further mixing and reaction may occur as the first and second substrates are passed through various other rollers, ultimately This is achieved when the substrate is finally passed through the rewinding rollers. The first substrate and the second substrate pass through the roller to take a longer or shorter path than the other substrate. As the two substrates pass through, further mixing and reaction occurs. The roller arrangement in the application device is The curable mixture is then cured or It can be hardened.

[0062] In a preferred embodiment, the process for producing the multilayer laminate structure comprises, for example, (I) at least (II) providing a first film substrate; and (II) providing at least one second film substrate. (III) providing, as a separate component, an isocyanate of SLAC; (IV) providing a component A, which is a hydroxy component, and a component B, which is a polyol component; The at least one first film substrate has an inner surface on at least a portion thereof coated with the isothiocyanate of the SLAC. applying an anate component to the isotropic layer on the inner surface of the at least one first film substrate; (V) forming a coating layer of a cyanate component; and (V) forming a coating layer of a SLAC polymer of the present invention. applying the all component to at least a portion of an interior surface of at least one second film substrate; forming a coating layer of a polyol component on the inner surface of at least one second film substrate; (VI) removing the isocyanate from the inner surface of the at least one first film substrate. A coating layer of a nate component is formed on the inner surface of the at least one second film substrate. The first film substrate and the second film substrate are in contact with the coating layer of the thiol component. The film substrates are then brought together to form the SLAC bond between the first substrate and the second substrate. (VII) forming an adhesive layer to form an uncured multi-layer laminate structure; and and curing the SLAC disposed between the first substrate and the second substrate to form a first substrate. and the second substrate together to form a cured bonded multi-layer laminate structure. Includes:

[0063] The application step (IV) of the above process is performed on the first layer to which the isocyanate component has not been applied. the outer surface or outer face of the first film substrate, and the inner surface or inner face of the second film substrate. The isocyanate component of SLAC is applied to at least a portion of one side of the first film substrate. The coating step (V) of the above process can be carried out at room temperature by The outer side or outer surface of the second film substrate to which the polyol component is not applied is the second film. At least a portion of one side of the second film substrate, such as the inside or inner surface of the film substrate, is provided with SL. This can be done by applying the polyol component of AC. According to step (VI), the inner surface of the first film substrate is bonded to the inner surface of the second film substrate. forming a layer of SLAC disposed between the first and second substrate layers; Step (VII) is a step of bonding the first and second substrates together to form a hardened layer structure. and (VI) adding the layered laminate structure to the SLAC layer to form a fused multilayer laminate structure. The method includes heating the composition to a temperature sufficient to cure the composition.

[0064] The application steps (IV) and (V) of the components of the SLAC adhesive composition or formulation This can be done by conventional means known in the art for applying the coating to films and substrates. Cut.

[0065] In step (VI) of the above process, S coated on a first film substrate The isocyanate component of the LAC was mixed with the polymer of the SLAC coated on the second film layer. The isocyanate component and the polyol component are mixed together, and the first A layer of SLAC is formed between the substrate and a second substrate to form an uncured multi-layer laminate structure.

[0066] At least a first film substrate and at least a second film substrate are brought into contact with each other. After the contacting step (VI) of the above process, step (VII) of the above process is followed. The SLAC layer disposed between the two substrates is then cured. A bond is formed between the first film substrate and the second film substrate, forming a cured multi-layer laminate. It is done.

[0067] Suitable substrates for the laminated structure include polyethylene films, polyamide films, and ethylene vinyl alcohol based films. Some films may optionally be coated with adhesive. The substrate has a surface on which an image can be printed with ink that can contact the composition. and the adhesive composition of the present invention bonds one or more substrates together.

[0068] Laminated structure One advantage of the SLAC of the present invention is that the resulting SLAC can be used in conventional adhesive formulations. By laminating various types of films using SLAC, we can achieve a high level of For example, SLAC can be used in a variety of processes to produce multilayer films. Plastic films, metallized films, aluminum foils, and other metallized and barrier Used to stack laminated structures, it is a composite film that is useful as a packaging material for food, medicine, detergent, etc. For example, the SLAC of the present invention can be used to produce multi-layer laminate structures. which is then packaged in a pouch, sachet, stand-up pouch, or other bag. manufacturing products or articles such as packaging components or containers, especially those used for packaging food It can be made.

[0069] In one embodiment, the laminate structure comprises: (a) a first film substrate; and (b) a second film substrate. a substrate (a); and (c) a film interposed between the first film substrate and the second film substrate, and a layer of SLAC bonding the film substrates (a) and (b). Suitable substrates include polymer films, metal foils, and metallized polymer films. Suitable polymer barrier films include polyethylene-based films, poly Examples of such films include amide-based films and ethylene vinyl alcohol-based films. Some films may optionally be coated with ink that may be in contact with the adhesive composition. The adhesive composition according to the present disclosure is used to bond one or more substrates together. In this state, the substrates are laminated to form a laminated structure. [Example]

[0070] The following examples are presented to further illustrate the invention and are not intended to be limiting unless otherwise specified. Unless otherwise indicated, all parts and and percentages are by weight.

[0071] Used in the examples (Inv. Ex.) and comparative examples (Comp. Ex.) of the present invention The various materials used are described in Table I.

[0072] [Table 1]

[0073] Polyol component B The SLAC of the present invention, referred to herein as the "inventive polyol component" ("IPC"), The coreactant used, Component B, was prepared according to the ingredients listed in Table II. R™ 101, ISONAT™ M125 and VORANOL™ CP75 5 was charged into the reactor, and then the contents of the reactor were stirred (mixed) while being heated. The temperature inside the reactor was maintained at 70-80°C for 2 hours. After 2 hours, the obtained mixture in the reactor The mixture was cooled to 40°C and then IP9001, VORANOL™ CP450 and S PECFLEX ACTIVE™ 2306 was charged into the reactor. The resulting mixture was stirred for 30 minutes, after which the resulting mixture formed an IPC. The IPC has an OH number of 136 and a viscosity of 14,000 mPa-s at 25°C.

[0074] [Table 2]

[0075] Laminated base material The laminates produced as described in the examples of this specification may be made of any of the following film substrates: It is made using one or more of: (1) unprinted 12 μm PET (PET); (2) 9 μm aluminum foil (Al); (3) 32% ethylene comonomer (PE-EVOH) 50 μm ethyl vinyl alcohol with a 5 μm EVOH layer containing A barrier polymer film comprising polyethylene co-extruded with polyamide (OPA).

[0076] The barrier films are assembled to produce a laminate, and the barrier films are Major Categories: (1) Metallized Laminate: Al / PET (unprinted, fully printed) (2) Polymer barrier laminates: PE-EVOH / PET and and PE-EVOH / OPA.

[0077] The laminates described in Table III were applied to the following substrates: (1) aluminum foil / PET; (2) PET / PET E-EVOH, and (3) OPA / PE-EVOH.

[0078] Comparative Examples A to E To prepare the laminates of Comparative Example A (baseline) and Comparative Example C listed in Table III The reference adhesive formulation used contained CR001 as a co-reactant; Comparative Examples B, D and The adhesive formulation used to make the E laminate uses CR002 as a co-reactant. Comparative Examples A, B, C, D and E using CR001 and CR002 are aromatic poly An adhesive formulation comprising an ester polyol but no aliphatic polyester polyol. The adhesive formulations used to prepare the laminates of Comparative Examples B, D, and E were aromatic poly(ethylene glycol). Adhesives of Comparative Examples B, D, and E contain silicone additives in addition to ester polyols. The compound must be redispersed immediately before the adhesive compound is used in the one-shot lamination process. There is.

[0079] Examples 1 to 5 The SLAC used to prepare the laminates of Examples 1 to 5 of the present invention was used as a co-reactant. Uses PC; no silicone additives added to SLAC; no need to redisperse SLAC stomach.

[0080] Laminate formation Table III shows laminates prepared using the adhesive components set forth in Tables I and II above. The laminated structure containing the adhesive system described in Table III has the following mechanical parameters: Nordmeccanica DUPLEX ONE-SHOT™ laminator Prepared: temperature of 45°C at dosing gap; application roll temperature of 55°C; nip roll Temperature: 55°C; Nip pressure: 2.5 Newtons (N); Lamination pressure: 1.5N; Unwinding tension: 90 Shore hardness at nip roll. As shown in Table III, the laminated OH part (e.g., a first substrate) is coated with an OH component (i.e., a polyol component), and a laminated NCO A part (e.g., a second substrate) is coated with an NCO component (i.e., an isocyanate component). Then, the two coated substrates are laminated together. The laminates are brought together at a nipping station to form a laminate. The weight is approximately 1.0 grams per square meter (g / m 2 ) Measuring temperature, application temperature , and nip temperatures are 50°C, 50°C, and 65°C, respectively.

[0081] Lamination speed The appearance of the laminate produced by the one-shot lamination process and laminator is shown in Fig. The laminates were visually inspected after fabrication to ensure they showed no visual defects such as bubbles or orange peeling. If not, the laminate structure is recorded on the speed monitor reading of the one-shot laminator. The maximum lamination speed was determined. Laminates made using the coreactant IPC of the present invention performed well. It showed excellent optical properties.

[0082] Table III shows the results of various adhesive formulations containing co-reactants CR 001 or CR 002. Lamination speed of the SLAC of the present invention containing IPC compared to other laminates made from The results of the lamination speed of the laminates produced are given below.

[0083] [Table 3]

[0084] Metallized laminates (i.e., unprinted, full print, printed window), and polymer barrier laminates, That is, PE-EVOH / PET and PE-EVOH / OPA are the adhesives of Comparative Examples A and B. When using adhesive systems, defects occur, which limits the lamination speed. Each type of structure has different properties that can be described as follows: For metallized laminate structures: The two main causes of defects observed at higher lamination line speeds are , poor wetting and air entrapment; in polymer barrier laminate structures, poor wetting and air entrapment , and CO2 generation are the three main causes of the defects observed (even at lower deposition rates). ).

[0085] The adhesive systems containing the CR002 coagent were compared with the adhesive formulations of Comparative Examples B, D, and E. Therefore, Comparative Examples B, D and E contain silicone-based additives that are not stable in The adhesive formulation requires that the formulation be redispersed immediately before use in the lamination process. Let's say.

[0086] Using a SLAC of the present invention containing a co-reactant IPC, as described in Table III, Depending on the laminate produced, the amount of defoamer, wetting agent or other additives in the solventless laminate adhesive formulation of the present invention may vary. Improved lamination speed on metallized and high barrier films without the use of additives Good is possible.

Claims

1. 1. A two-component solventless laminating adhesive composition comprising: (A) at least one isocyanate component containing at least one isocyanate; 、 (B) (Bi) at least one amine-initiated polyol; (Bii) at least one aliphatic polyester polyol; and (Biii) at least one polyol containing at least one polyether polyol and an all component.

2. The at least one aliphatic polyester polyol is a mixture of an aliphatic polycarboxylic acid and a polycarboxylic acid. wherein the amine-initiated polyol is a compound derived from a polyol of the formula (I): having a structure; 【Chemistry 1】 The at least one polyether polyol may be polypropylene glycol, polyether Tramethylene ether glycol, polybutylene oxide polyol and their copolymers 10. The compound of claim 1, wherein the compound is selected from the group consisting of: A two-component solventless laminating adhesive composition.

3. The concentration of the at least one amine-initiated polyol is from 6 weight percent to 40 weight percent. the concentration of said at least one aliphatic polyester polyol is 10 parts by weight; 10 to 30 weight percent of said at least one polyether polyol; 10. The two-component solventless composition of claim 1, wherein the concentration is from 40 weight percent to 60 weight percent. Laminating adhesive compositions.

4. A two-component solventless laminating adhesive composition, the ratio of A:B being from 100:100 to 100:8 2. The two-component solventless laminating adhesive composition of claim 1, wherein

5. A process for making a two-component solventless laminating adhesive composition, (A) at least one isocyanate component containing at least one isocyanate; 、 (B) (Bi) at least one amine-initiated polyol; (Bii) at least one aliphatic polyester polyol; and (Biii) a polyol composition comprising at least one polyether polyol; and at least one polyol component comprising the polymer.

6. 1. A multi-layer laminate film composite structure comprising: (a) at least one first substrate layer; (b) at least one second substrate layer; (c) the adhesive layer according to claim 1 disposed between the first substrate layer and the second substrate layer. a layer of an adhesive composition, wherein the adhesive is cured to bond the first substrate layer to the second substrate. A multi-layer laminated film composite structure bonded to the material layers.

7. 7. A process for manufacturing the multilayer laminate structure of claim 6, comprising: (I) providing at least a first substrate; (II) providing at least a second substrate; (III) providing the solventless laminating adhesive composition of claim 1; (IV) The at least one isocyanate is applied to at least a portion of one surface of the first substrate. a first layer of an anate component is applied to the at least one substrate disposed on the first substrate; forming a film layer of the isocyanate component; (V) applying the at least one polyol to at least a portion of one surface of the second substrate; a coating layer of the polyol component disposed on the second substrate; forming a film layer of (VI) dissolving a layer of at least one isocyanate component on the surface of the first substrate, contacting a coating layer of at least one polyol component on the surface of a second substrate; At least one isocyanate component and a polyisocyanate component are disposed between the first substrate and the second substrate. forming a composite adhesive formulation layer containing all components to form a layered laminate structure; (VII) curing the adhesive formulation between the first substrate and the second substrate, The first substrate is attached to the second substrate via a bonded adhesive layer to form a bonded multi-layer stack. forming a layer structure.

8. A laminate structure comprising the two-component solventless laminating adhesive composition of claim 1.

9. 10. The laminate structure of claim 8, further comprising a polymeric barrier substrate or a metal / metallized substrate.

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