Method for producing polyurethane polyisocyanate

Abstract

To provide a method for producing polyurethane polyisocyanate having stable quality without needing to dispose of unreacted isocyanate monomer discharged from the production process.　The method for producing polyurethane polyisocyanate includes: a step 1 for reacting TDI (o) having a proportion of 2,4-TDI of 50 mass% to 90 mass% with a polyol (p) to obtain a composition containing polyurethane polyisocyanate (A1) and TDI (o '); a step 2 for removing the TDI (o ') from the composition obtained in step 1; a step 3 for adding 2,4-TDI to at least a part of the TDI (o ') to obtain a composition containing polyurethane polyisocyanate (A2) and TDI (q ') by reacting TDI (q) adjusted to a 2,4-TDI content of 50 mass% to 90 mass% with polyol (r); and a step 4 for removing the TDI (q ') from the composition obtained in step 3.

Description

Method for producing polyurethane polyisocyanate

[0001] The present invention relates to a method for producing polyurethane polyisocyanates.

[0002] Laminates used in various packaging materials, labels, etc. are imparted with design, functionality, storage stability, convenience, transport resistance, etc. by laminating a wide variety of substrates such as plastic films, metal foils, and paper. Packaging materials obtained by molding such laminates into bags are used as packaging materials in a variety of fields, including food, pharmaceuticals, detergents, etc. Urethane reactive two-component adhesives (hereinafter sometimes referred to as two-component curing adhesives or reactive adhesives) have been widely used to manufacture such laminates.

[0003] Some urethane reactive two-component curing adhesives use components containing a certain amount of isocyanate monomer, such as isocyanate prepolymers. However, there is a movement to restrict the use of isocyanate monomer from the viewpoint of occupational safety and health. The European Commission adopted the REACH regulation, which prohibits the marketing of products containing more than 0.1% by weight of isocyanate monomer unless certain requirements are met.

[0004] There are other concerns about isocyanate monomers. When two-component curing adhesives containing aromatic isocyanate prepolymers are used to manufacture laminates for food packaging, unreacted aromatic isocyanate monomers may remain in the adhesive layer. The isocyanate monomers react with surrounding water to form primary aromatic amines (PAA), which may migrate through the film and leach into the contents (food). Due to concerns about the toxicity of PAA to the human body, various regulations have been put in place, including the European Commission's detection limit for PAA in its regulations on plastic materials and articles intended for food contact.

[0005] Since PAA reacts with unreacted aromatic isocyanate present in the vicinity, even if aromatic isocyanate remains in the adhesive layer, the concentration of PAA gradually decreases and eventually falls below the detection limit. However, from the viewpoint of the production efficiency of laminates for food packaging, it is preferable that the initial value of aromatic isocyanate monomer remaining in the adhesive layer is low.

[0006] Methods for reducing the content of isocyanate monomers have been studied in the past. For example, Patent Document 1 discloses a method for forming an isocyanate-functional prepolymer with a low residual isocyanate content, which comprises: (a) reacting a polyol selected from the group consisting of polyether polyols, polyester polyols, polyester polyether polyols, acrylic polyols, glycols, and mixtures thereof with an isocyanate monomer to form a reaction mixture containing a prepolymer having an NCO content of 2.5 to 11.5 wt % and an average NCO functionality in the range of 2.0 to 3.0; and (b) passing the reaction mixture containing the prepolymer and unreacted isocyanate through a short-path evaporator to remove the unreacted isocyanate to an amount of less than 0.15 wt %.

[0007] Japanese Patent Application Laid-Open No. 2002-265552

[0008] When residual isocyanate monomer is removed from the isocyanate-functional prepolymer using such methods, unreacted isocyanate monomer is discharged from the manufacturing process. There is a need for a method for producing polyurethane polyisocyanates of stable quality without discarding the unreacted isocyanate monomer discharged from such manufacturing processes.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing polyurethane polyisocyanates of stable quality without discarding unreacted isocyanate monomer discharged from the production process.

[0010] That is, the present invention provides a method for producing a composition comprising: Step 1 of reacting toluene diisocyanate (o) containing 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, wherein the proportion of 2,4-toluene diisocyanate is 50% by mass or more and 90% by mass or less, with a polyol (p) under conditions in which the number of isocyanate groups in the toluene diisocyanate (o) is at least twice as many as the number of hydroxyl groups in the polyol (p), thereby obtaining a composition containing a polyurethane polyisocyanate (A1) and toluene diisocyanate (o'); and Step 2 of removing the toluene diisocyanate (o') from the composition obtained in Step 1. The present invention relates to a method for producing a polyurethane polyisocyanate, comprising: Step 3 of reacting toluene diisocyanate (q), which is prepared by adding 2,4-toluene diisocyanate to at least a part of toluene diisocyanate (o') so that the 2,4-toluene diisocyanate content is adjusted to 50% by mass or more and 90% by mass or less, with a polyol (r) under conditions such that the number of isocyanate groups in the toluene diisocyanate (q) is at least twice as many as the number of hydroxyl groups in the polyol (r), to obtain a composition containing a polyurethane polyisocyanate (A2) and toluene diisocyanate (q'); and Step 4 of removing the toluene diisocyanate (q') from the composition obtained in Step 3.

[0011] According to the present invention, it is possible to provide a method for producing polyurethane polyisocyanates of stable quality without discarding unreacted isocyanate monomers discharged from the production process.

[0012] <Method for Producing Polyurethane Polyisocyanate (A)> The method for producing the polyurethane polyisocyanate (A) of the present invention comprises the following steps: (Step 1) Step 1 is a step of reacting toluene diisocyanate (o) with a polyol (p) under conditions such that the number of isocyanate groups in the toluene diisocyanate (o) is at least 2 times, more preferably 2 to 20 times, the number of hydroxyl groups in the polyol (p), to obtain a composition containing polyurethane polyisocyanate (A1) and unreacted toluene diisocyanate (o') of the toluene diisocyanate (o) that has not reacted with the polyol (p).

[0013] The toluene diisocyanate (o) is a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and the proportion of 2,4-toluene diisocyanate in the toluene diisocyanate (o) is 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 80% by mass or less. Such toluene diisocyanate (o) is easy to handle and allows for efficient production of the polyurethane polyisocyanate (A).

[0014] As the polyol (p), conventionally known polyols can be used, for example, glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;

[0015] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol; polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as glycol or a trifunctional or tetrafunctional aliphatic alcohol;

[0016] Polyester polyols (1) are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the like with polyhydric alcohols such as the glycols, glycerin, trimethylolpropane, and pentaerythritol; polyester polyols (2) are obtained by reacting a bifunctional polyol such as glycol, dimer diol, or bisphenol with a polycarboxylic acid; polyester polyols (3) are obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; polyester polyols (4) are obtained by reacting a bifunctional polyol with a trifunctional or tetrafunctional aliphatic alcohol and a polycarboxylic acid; polyester polyols (5) are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;

[0017] Polyurethane polyol (1) obtained by polymerizing at least one selected from bifunctional polyols and trifunctional or tetrafunctional aliphatic alcohols with an isocyanate compound; polyether urethane polyol (2) obtained by further polymerizing a polyether polyol with an isocyanate compound; polyester polyurethane polyol (3) obtained by polymerizing polyester polyols (1) to (5) with an isocyanate compound; polyester polyether polyurethane polyol (4) obtained by reacting at least one of polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound;

[0018] Examples include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, and castor oil-based polyols such as 5 to 50 mol alkylene oxide adducts of castor oil, and mixtures thereof, and these may be used alone or in combination of two or more.

[0019] Examples of polycarboxylic acids used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; and methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate.

[0020] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0021] Alicyclic polybasic acids such as 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic-1,2-anhydride, himic anhydride, and HET acid anhydride can be mentioned, and these can be used alone or in combination of two or more.

[0022] As the isocyanate compound used in the synthesis of the polyurethane polyols (1) to (4), known aromatic, araliphatic, aliphatic and alicyclic diisocyanates can be used alone or in combination of two or more.

[0023] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also known as polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also known as PPDI), 2,4-tolylene diisocyanate, and the like. Examples of the isocyanate include, but are not limited to, 2,6-tolylene diisocyanate (also known as TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0024] The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0025] Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI), but are not limited to these.

[0026] Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI), but are not limited to these.

[0027] The reaction between polyisocyanate (o) and polyol (p) is carried out, for example, at a temperature of 50°C to 100°C or less. After charging the polyisocyanate (o) into a reactor, it is heated to a predetermined temperature (step 1-1), and polyol (p) is added dropwise thereto over several hours (step 1-2). After the polyol (p) has been added dropwise, urethane formation is allowed to proceed over several hours (step 1-3). The time spent in these steps can be adjusted as appropriate; for example, step 1-1 can be adjusted to 30 minutes to 2 hours, step 1-2 can be adjusted to 1 hour to 5 hours, and step 1-3 can be adjusted to 1 hour to 10 hours. In this case, a urethane formation catalyst may or may not be used. Step 1 is carried out until the urethane formation reaction is completed, and is terminated when the NCO % of the system no longer changes (the change after 1 hour is within a range of ±0.05%).

[0028] (Step 2) In step 2, toluene diisocyanate (o') is removed from the composition containing the polyurethane polyisocyanate (A1) obtained in step 1 and toluene diisocyanate (o') to obtain a polyurethane polyisocyanate (A1) having an extremely reduced content of monomeric diisocyanate. The toluene diisocyanate (o') is removed by a method of distilling the toluene diisocyanate (o') under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, or the like. The degree of reduced pressure and the distillation temperature are adjusted as appropriate, but are, for example, 0.1 mbar or less and 120°C to 190°C. The removed toluene diisocyanate (o') is temporarily stored.

[0029] Step 2 is, for example, carried out until the content of toluene diisocyanate (o') in the total amount of polyurethane polyisocyanate (A1) and toluene diisocyanate (o') is 1.0 mass% or less. This allows for the production of a polyurethane polyisocyanate (A1) with excellent work environment suitability. Step 2 is preferably carried out until the content of toluene diisocyanate (o') in the total amount of polyurethane polyisocyanate (A1) and toluene diisocyanate (o') is 0.5 mass% or less, and preferably 0.1 mass% or less. The content of toluene diisocyanate (o') can be measured, for example, by gas chromatography using an internal standard in accordance with ASTM D 3432. Alternatively, it can also be measured by liquid chromatography under the following conditions.

[0030] Apparatus: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40°C Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds 3. Dilute appropriately with eluent (mobile phase) 4. Pass through a 0.2 μm filter to prepare the measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0031] (Step 3) Step 3 is a step of reacting toluene diisocyanate (q) with polyol (r) under conditions in which the number of isocyanate groups in toluene diisocyanate (q) is 2 times or more, more preferably 2 to 20 times, the number of hydroxyl groups in polyol (r), to obtain a composition containing polyurethane polyisocyanate (A2) and unreacted toluene diisocyanate (q′) of toluene diisocyanate (q) that has not reacted with polyol (p).

[0032] Toluene diisocyanate (q) is prepared by adding 2,4-toluene diisocyanate, and if necessary, 2,6-toluene diisocyanate, to at least a portion of the toluene diisocyanate (o') recovered in step 2, so that the proportion of 2,4-toluene diisocyanate in the toluene diisocyanate (q) is adjusted to 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 80% by mass or less. As the polyol (r), the same polyols as those exemplified as the polyol (p) can be used. Only one type may be used, or two or more types may be used in combination.

[0033] Due to the difference in reactivity of the isocyanate groups at the 2-, 4-, and 6-positions of toluene diisocyanate, 2,4-toluene diisocyanate is preferentially consumed in the urethanization reaction in step 1, and therefore the toluene diisocyanate (o') recovered in step 2 has a lower 2,4-toluene diisocyanate content than the toluene diisocyanate (o). Because 2,4-toluene diisocyanate and 2,6-toluene diisocyanate have different symmetries, if the toluene diisocyanate recovered in step 2 is reused as is for the synthesis of polyurethane polyisocyanate (A), there is a risk of variations in the physical properties of the polyurethane polyisocyanate (A) obtained from different lots. Furthermore, if an attempt is made to use only 2,4-toluene diisocyanate (or only 2,6-toluene diisocyanate) in the production of polyurethane polyisocyanate (A), such toluene diisocyanate is difficult to handle, making it impossible to efficiently produce polyurethane polyisocyanate (A).

[0034] In the present invention, by reusing the recovered toluene diisocyanate while adjusting the contents of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate to fall within a certain range, it is possible to efficiently produce a polyurethane polyisocyanate (A) with reduced fluctuations in physical properties.

[0035] The reaction of polyisocyanate (q) with polyol (r) can be carried out in the same manner as in step 1. In this case, a urethanization catalyst may or may not be used. Step 3 is carried out until the urethanization reaction is completed, and is terminated when the NCO% of the system no longer changes (the change after 1 hour falls within the range of ±0.05%).

[0036] (Step 4) In step 4, in the same manner as in step 2, toluene diisocyanate (q') is removed from the composition containing the polyurethane polyisocyanate (A2) obtained in step 3 and toluene diisocyanate (q') to obtain a polyurethane polyisocyanate (A2) having an extremely reduced content of monomeric diisocyanate. The toluene diisocyanate (q') is removed by distilling the toluene diisocyanate (q') under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, or the like. The degree of reduced pressure and the distillation temperature are adjusted as appropriate, but are, for example, 0.1 mbar or less and 120°C to 190°C. The removed toluene diisocyanate (q') is temporarily stored.

[0037] Step 4 is performed, for example, until the content of toluene diisocyanate (q') in the total amount of polyurethane polyisocyanate (A2) and toluene diisocyanate (q') is 1.0 mass% or less. Step 4 is also preferably performed until the content of toluene diisocyanate (o') in the total amount of polyurethane polyisocyanate (A1) and toluene diisocyanate (o') is 0.5 mass% or less, and also preferably until it is 0.1 mass% or less.

[0038] Thereafter, in the same manner as in step 3, 2,4-toluene diisocyanate and, if necessary, 2,6-toluene diisocyanate are added to at least a part of the toluene diisocyanate (q') to prepare toluene diisocyanate (s) adjusted so that the proportion of 2,4-toluene diisocyanate is 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 80% by mass or less, and a polyol (t) is mixed in such a manner that the number of isocyanate groups in the toluene diisocyanate (s) is at least twice as many as the number of hydroxyl groups in the polyol (t). , more preferably 2 to 20 times, to obtain a composition containing polyurethane polyisocyanate (A3) and unreacted toluene diisocyanate (s') of toluene diisocyanate (s) that has not reacted with polyol (t), and a step of removing toluene diisocyanate (s') from the composition containing polyurethane polyisocyanate (A3) and toluene diisocyanate (s') obtained in step 3' in the same manner as step 4 to obtain polyurethane polyisocyanate (A3). This allows efficient production of polyurethane polyisocyanate (A) with stable physical properties.

[0039] (Variations) In the method for producing polyurethane polyisocyanate (A) of the present invention, the produced polyurethane polyisocyanates (A1), (A2), (A3), etc. may be the same or different. For example, the polyols (p), (r), and (t) may all be trimethylolpropane, and the resulting polyurethane polyisocyanates (A1), (A2), and (A3) may all be reaction products of toluene diisocyanate and trimethylolpropane (so-called adducts of toluene diisocyanate and trimethylolpropane). Alternatively, the polyol (p) may be trimethylolpropane, the polyol (r) may be a polyester polyol, and the polyol (t) may be a polyether polyol. Alternatively, the polyol (p) may be a polyester polyol, the polyol (r) may be a mixture of a polyester polyol and a polyether polyol, and the polyol (t) may be a polyether polyol.

[0040] The phrase "the polyurethane polyisocyanates (A1) and (A2) to be produced are the same" means that the difference between the proportion of 2,4-toluene diisocyanate in toluene diisocyanate (o) and the proportion of 2,4-toluene diisocyanate in toluene diisocyanate (q) is within the range of manufacturing error (±5% by mass), the polyols constituting polyol (p) and the proportions thereof constituting polyol (r) are within the range of manufacturing error (±3% by mass), and the difference between the molar ratio of isocyanate groups in toluene diisocyanate (o) to the hydroxyl groups in polyol (p) and the molar ratio of isocyanate groups in toluene diisocyanate (q) to the hydroxyl groups in polyol (r) is within the range of manufacturing error (±0.2).

[0041] The toluene diisocyanates (o'), (q'), and (s') may be stored in the same container or in different containers. Toluene diisocyanates recovered from the production process of the same type of polyurethane polyisocyanate (A) may be stored in the same container, while other recovered toluene diisocyanates may be stored in different containers.

[0042] In step 2, step 4, and step 4', the removal of toluene diisocyanates (o'), (q'), and (s') may be carried out once or in multiple batches (by passing through multiple distillation apparatuses connected in series). For example, toluene diisocyanate (o'-1) may be removed from the composition obtained in step 1 using distillation apparatus 1, and then toluene diisocyanate (o'-2) may be removed from the composition containing polyurethane polyisocyanate (A1) recovered from distillation apparatus 1 using distillation apparatus 2, thereby obtaining a polyurethane polyisocyanate (A1) having a small amount of residual isocyanate monomer.

[0043] In this case, toluene diisocyanate (o'-1) and toluene diisocyanate (o'-2) may be collected and stored in the same container, or may be collected and stored in different containers. When toluene diisocyanate (o'-1) and toluene diisocyanate (o'-2) are stored in different containers, toluene diisocyanate (q) may be prepared by adding 2,4-toluene diisocyanate and, if necessary, 2,6-toluene diisocyanate to either toluene diisocyanate (o'-1) or toluene diisocyanate (o'-2), or may be prepared by adding 2,4-toluene diisocyanate and, if necessary, 2,6-toluene diisocyanate to toluene diisocyanate (o'-1) and toluene diisocyanate (o'-2).

[0044] The toluene diisocyanates (o'), (q'), and (s') recovered in step 2, step 4, step 4', etc. may be purified before being reused. Examples of the purification method include, but are not limited to, filtration and distillation. A plurality of methods may be combined in the purification step.

[0045] The polyurethane polyisocyanate (A) obtained in step 2, step 4, step 4', etc. is used after diluting with an organic solvent, if necessary.

[0046] <Polyisocyanate Composition> The polyisocyanate composition of the present invention contains the polyurethane polyisocyanate (A) obtained by the above-mentioned method. The polyisocyanate composition may also contain a polyisocyanate compound (B) other than the polyurethane polyisocyanate (A). Even when the polyisocyanate composition contains the polyisocyanate compound (B), the content of the diisocyanate monomer is 1.0 mass% or less of the polyisocyanate composition.

[0047] Examples of the polyisocyanate compound (B) include biuret compounds, nurate compounds, adduct compounds, allophanate compounds, carbodiimide-modified compounds, and uretdione-modified compounds of at least one diisocyanate selected from aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The polyisocyanate compound (B) can be used alone or in combination of two or more.

[0048] The aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be the same as those exemplified as the isocyanate compounds used in the synthesis of the polyurethane polyols (1) to (4) (one example of the polyol (p)).

[0049] When the polyisocyanate composition (X) contains the polyisocyanate compound (B) in addition to the polyurethane polyisocyanate (A), the content thereof can be adjusted appropriately. As an example, the proportion of the polyurethane polyisocyanate (A) in the total amount of the polyurethane polyisocyanate (A) and the polyisocyanate compound (B) is 50 mass% or more.

[0050] The polyisocyanate composition of the present invention may be diluted with an organic solvent such as an ester such as ethyl acetate, butyl acetate, or cellosolve acetate; a ketone such as acetone, methyl ethyl ketone, isobutyl ketone, or cyclohexanone; an ether such as tetrahydrofuran or dioxane; an aromatic hydrocarbon such as toluene or xylene; a halogenated hydrocarbon such as methylene chloride or ethylene chloride; dimethyl sulfoxide; or dimethyl sulfamide.

[0051] The polyisocyanate composition of the present invention can be used as a two-component curing composition in combination with an isocyanate-reactive composition containing a compound reactive with isocyanate. Examples of the compound reactive with isocyanate include polyether polyol, polyester polyol, polyester polyether polyol, polyurethane polyol, polyester polyurethane polyol, polyether polyurethane polyol, vegetable oil polyol, sugar alcohol, polycarbonate polyol, acrylic polyol, hydroxyl group-containing olefin resin, hydroxyl group-containing fluororesin, and (poly)alkanolamine.

[0052] Such two-component curing compositions can be used, for example, as adhesives, coating agents, sealants, elastomers, and the like.

[0053] <Adhesive> The adhesive of the present invention is a two-component curing adhesive containing a polyisocyanate composition (X) and a polyol composition (Y).

[0054] (Polyisocyanate Composition (X)) The polyisocyanate composition (X) contains the polyurethane polyisocyanate (A) described above. The polyisocyanate composition (X) may also contain a polyisocyanate compound (B) other than the polyurethane polyisocyanate (A). Examples of the polyisocyanate compound (B) include biuret compounds, nurate compounds, allophanate compounds, carbodiimide-modified compounds, and uretdione-modified compounds of at least one diisocyanate selected from aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The polyisocyanate compound (B) can be used alone or in combination of two or more.

[0055] The aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be the same as those exemplified as the isocyanate compounds used in the synthesis of the polyurethane polyols (1) to (4) (one example of the polyol (p)).

[0056] When the polyisocyanate composition (X) contains the polyisocyanate compound (B) in addition to the polyurethane polyisocyanate (A), the content thereof can be adjusted appropriately. As an example, the proportion of the polyurethane polyisocyanate (A) in the total amount of the polyurethane polyisocyanate (A) and the polyisocyanate compound (B) is 50 mass% or more.

[0057] The polyisocyanate composition (X) used in the adhesive of the present invention has a content of diisocyanate monomers such as aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the polyurethane polyisocyanate (A), of 1.0 mass % or less.

[0058] When the adhesive of the present invention is used as a solventless two-component curing adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to a range of 100 to 50,000 mPas, more preferably 500 to 20,000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by adjusting the structure of the polyurethane polyisocyanate (A) (the polyols (p), (r), and (t) used) or by using a polyisocyanate compound (B) in combination. The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer with a cone and plate of 1° x 50 mm diameter and a shear rate of 100 sec. －１ , can be measured at 40°C ± 1°C.

[0059] (Polyol composition (Y)) The polyol composition (Y) contains a polyol compound (C) having multiple hydroxyl groups. The polyol compound (C) is not particularly limited, and any polyol compound typically used in a urethane-reactive two-component curing adhesive can be used.

[0060] Specific examples of the polyol compound (C) include polyether polyols, polyester polyols, polyester polyether polyols, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, vegetable oil polyols, sugar alcohols, polycarbonate polyols, acrylic polyols, hydroxyl group-containing olefin resins, and hydroxyl group-containing fluororesins.

[0061] Examples of polyether polyols include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol; and trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and polypropylene glycol triols. Polypropylene polyol is preferably used.

[0062] Polyester polyols are reaction products of polyhydric alcohols and polycarboxylic acids. The polyhydric alcohols used in the synthesis of polyester polyols may be diols or tri- or higher functional polyols. Furthermore, polyester polyether polyols using the polyether polyols described above or polyester polyurethane polyols using polyurethane polyols described below may also be used. Examples of diols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0063] Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; modified polyether diols obtained by ring-opening polymerization of aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0064] Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactanoids and ε-caprolactone;

[0065] bisphenols such as bisphenol A and bisphenol F;

[0066] Examples include alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F.

[0067] Tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0068] modified polyether polyols obtained by ring-opening polymerization of aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0069] Examples include lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols with various lactones such as ε-caprolactone.

[0070] Examples of polycarboxylic acids used in the synthesis of polyester polyols include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids; and polybasic acids such as dimer acid.

[0071] Examples of the vegetable oil polyol include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an alkylene oxide 5 to 50 mole adduct of castor oil.

[0072] Polyurethane polyols are reaction products of low-molecular-weight or high-molecular-weight polyols and polyisocyanate compounds. Examples of low-molecular-weight polyols include the same polyhydric alcohols exemplified as raw materials for polyester polyols. Examples of high-molecular-weight polyols include polyether polyols and polyester polyols. Examples of polyisocyanate compounds that can be used include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates exemplified as isocyanate compounds used in the synthesis of polyurethane polyols (1) to (4) (examples of polyol (p)), as well as compounds exemplified as polyisocyanate compound (B).

[0073] Examples of sugar alcohols include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0074] (Amine Compound (D)) The polyol composition (Y) may contain an amine compound (D) having an amino group. In this specification, the amino group refers to an amine compound having an NH ２ group or NHR group (R is an alkyl group or aryl group which may have a functional group).

[0075] As the amine compound (D), known compounds can be used without any particular limitation, and examples thereof include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspirodoundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0076] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine,

[0077] amine compounds (D1) having a plurality of amino groups, such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines with the above-mentioned various isocyanate components;

[0078] primary or secondary alkanolamines (D2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0079] Examples thereof include primary or secondary amines (D3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0080] The amount of the amine compound (D) to be blended is preferably such that the amine value of the polyol composition (Y) is 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0081] In this specification, the amine value refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using known methods. When the chemical structure of the amine compound (D) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to known amine value measurement methods, for example, JIS K7237-1995.

[0082] (Monool Compound (E)) The polyol composition (Y) may contain a monool compound (E) having one alcoholic hydroxyl group. The main chain of the monool compound (E) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used. The main chain of the monool compound (E) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably present at the terminal of the molecular chain.

[0083] Specific examples of the monool compound (E) include aliphatic monools such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 to C50), oleyl alcohol, and isomers thereof;

[0084] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decitol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and isomers thereof;

[0085] aromatic aliphatic monools such as benzyl alcohol,

[0086] Examples of the polyoxyalkylene monool include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.

[0087] When the two-component curing adhesive of the present invention is used as a solventless type, the viscosity of the polyol composition (Y) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the polyol composition (Y) can be adjusted by the skeleton of the polyol compound (C) or the plasticizer described below. When adjusting the skeleton of the polyol compound (C), the viscosity can be reduced by using, for example, a polypropylene polyol or a polyester polyol obtained by reacting an aliphatic carboxylic acid with a polyol. Alternatively, the viscosity can be increased by using a polyester polyol obtained by reacting an aromatic carboxylic acid with a polyol.

[0088] (Other Components of the Adhesive) The two-component curing adhesive of the present invention may contain components other than those described above. The other components may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the polyol composition (Y) immediately before application of the adhesive. Each component will be described below.

[0089] (Catalyst) Examples of the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0090] Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.

[0091] Examples of inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.

[0092] Examples of the organometallic catalyst include organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organic tin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organic nickel compounds such as nickel octylate and nickel naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one of alcohols having 2 to 10 carbon atoms as a ligand.

[0093] Examples of the amine catalyst include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropyl propanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 , 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

[0094] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is more effective in accelerating curing.

[0095] Examples of quaternary ammonium salts include hydroxy salts of alkyl ammonium, aromatic ammonium, etc., alkyl acid salts, halide salts, etc. Examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, etc.

[0096] (Acid Anhydride) Examples of the acid anhydride include alicyclic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc., and can be used alone or in combination of two or more. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methylnadic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and the like.

[0097] Alternatively, the acid anhydride may be a compound modified with a glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may also be used.

[0098] Alternatively, among the compounds described above as the acid anhydride (B), a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, may be used. Examples of compounds copolymerizable with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring, such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These compounds may be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0099] (Coupling Agent) Examples of the coupling agent include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.

[0100] Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0101] Examples of titanate coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0102] Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

[0103] (Pigment) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0104] Examples of extender pigments include precipitated barium sulfate, powdered barium sulfate, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine powdered silica (white carbon), ultrafine powdered anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow ochre.

[0105] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Lake 4R; soluble azo pigments such as Lake C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as Phthalocyanine Blue and Phthalocyanine Green; various chlorine dye lakes such as Rhodamine Lake and Methyl Violet Lake; various mordant dye pigments such as Quinoline Lake and Fast Sky Blue; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, and Perinone pigments; various quinacridone pigments such as Synchasia Red B; various dioxazine pigments such as Dioxazine Violet; various condensed azo pigments such as Chromophtal; and aniline black.

[0106] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as iron blue; various metal oxides such as titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, and the like.

[0107] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0108] The pigment to be used may be selected appropriately depending on the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferably used as black pigments.

[0109] The blending amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of nonvolatile components of the polyol composition (X) and the polyisocyanate composition (Y), and is more preferably 10 to 300 parts by mass in order to improve adhesion and blocking resistance.

[0110] (Plasticizer) Examples of the plasticizer include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0111] Examples of the phthalic acid plasticizer include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0112] Examples of the fatty acid plasticizer include adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate and di-(2 Sebacic acid plasticizers such as di-n-butyl maleate, di-(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of suitable plasticizers include itaconic acid-based plasticizers such as itaconate and di-(2-ethylhexyl)itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerin monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0113] Examples of aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate.

[0114] Examples of phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0115] Examples of polyol-based plasticizers include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate; and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

[0116] Examples of epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, di-2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0117] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0118] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0119] Other examples of the plasticizer include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers, etc. These plasticizers can be used alone or in combination of two or more.

[0120] (Phosphate Compound) Examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate.

[0121] (Form of adhesive) The two-component curing adhesive of the present invention may be either a solvent-based or solventless type. In this specification, a "solvent-based" adhesive refers to a form used in a so-called dry lamination method, in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating, and then bonded to another substrate. Either or both of the polyisocyanate composition (X) and the polyol composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention.

[0122] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during production of the components of the polyisocyanate composition (X) and the polyol composition (Y) may also be used as a diluent during coating.

[0123] In this specification, a "solventless" adhesive refers to a form of adhesive in which the polyisocyanate composition (X) and the polyol composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.; ethers such as tetrahydrofuran, dioxane, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc.; highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone; and which is used in a method in which the adhesive is applied to a substrate and then bonded to another substrate without going through a step of heating in an oven or the like to volatilize the solvent, i.e., a so-called non-solvent lamination method. If the organic solvent used as a reaction medium during the production of the components of the polyisocyanate composition (X) or the polyol composition (Y) or the raw materials thereof cannot be completely removed, and trace amounts of organic solvent remain in the polyisocyanate composition (X) or the polyol composition (Y), the composition is considered to be substantially free of organic solvent. Furthermore, if the polyol composition (Y) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (X) to become part of the coating film, and therefore does not need to be volatilized after application. Therefore, such a form is also treated as a solventless adhesive, and the low-molecular-weight alcohol is not considered an organic solvent.

[0124] The two-component curing adhesive of the present invention is preferably used by blending the polyisocyanate composition (X) and the polyol composition (Y) so that the ratio [NCO] / [OH], where [NCO] is the number of moles of isocyanate groups contained in the polyisocyanate composition (X) and [OH] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity at the time of application.

[0125] <Laminate> The laminate of the present invention can be obtained, for example, by a method including a two-liquid mixing step in which a polyisocyanate composition (X) and a polyol composition (Y) are mixed in advance, then coated on a first substrate, and then a second substrate is laminated on the coated surface, and the adhesive layer is cured, or by a method including a two-liquid separate coating step in which a polyisocyanate composition (X) and a polyol composition (Y) are separately coated on a first substrate and a second substrate, and then the coated surfaces are brought into contact with each other and pressure-bonded to laminate the first substrate and the second substrate, and the adhesive layer is cured. There are no particular restrictions on the film used, and a film can be appropriately selected depending on the application.

[0126] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, OPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin films such as gas-barrier heat-sealable films in which an olefin-based heat-sealable resin layer is provided on one or both sides of a resin having gas-barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0127] It is also preferable to use biomass films, biodegradable films, and recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components. Biomass films, biodegradable films, and recycled plastic films are sold by various companies, and films certified in various countries can also be used, such as film sheets listed in the list of biomass-certified products listed by the Japan Organics Recycling Association, films listed in the list of Eco Mark-certified products listed by the Japan Environment Association, and films bearing the symbol mark designated by the Japan Bioplastics Association.

[0128] (Biomass Film) Specific examples of well-known biomass films include those made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0129] For example, as an alternative to conventional polyethylene terephthalate films made from petroleum-based raw materials, films containing biomass polyesters and biomass polyethylene terephthalates, which have biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acids as the dicarboxylic acid units, are known.

[0130] The dicarboxylic acid units of the biomass polyester use dicarboxylic acids derived from fossil fuels. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without limitation as dicarboxylic acids. Furthermore, the biomass polyester may be a copolymer polyester containing, in addition to the diol and dicarboxylic acid components, a bifunctional oxycarboxylic acid or a third copolymer component, such as at least one polyfunctional compound selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polycarboxylic acid and / or its anhydride, and a trifunctional or higher oxycarboxylic acid, to form a crosslinked structure.

[0131] Also, for example, as an alternative to conventional polyolefin films using petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films containing polyethylene resins made from biomass-derived ethylene glycol are known. The polyethylene resin is not particularly limited except that the biomass-derived ethylene glycol is used as part of the raw material, and examples include ethylene homopolymers and copolymers of ethylene and α-olefins containing ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units), and these can be used alone or in combination of two or more.

[0132] The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples thereof include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among these, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of further reducing the risk of damage such as holes and tears even when films are rubbed against each other, and has a density of 0.910 to 0.925 g / cm. ３ More preferred is a linear low density polyethylene resin in which

[0133] Biomass films made from biomass raw materials classified by the biomass plastic content specified in ISO 16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 10 particles, and this rate is the same for atmospheric carbon dioxide, so this rate remains the same even in plants that fix carbon dioxide through photosynthesis. Therefore, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the plant-derived resin content in the resin, i.e., the biomass plastic content, can be determined.

[0134] Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866, include products manufactured by Braskem under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0135] Films and sheets containing starch, a biomass material, or polylactic acid are also known. These can be selected and used appropriately depending on the application.

[0136] The biomass film may be a laminate of multiple biomass films or a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched or stretched, and their manufacturing method is not limited.

[0137] (Biodegradable Films) Specific examples of well-known biodegradable films include those made from commonly available biodegradable resins. Examples include polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resins, aliphatic polyester resins, and aliphatic aromatic polyester resins. These biodegradable resins may be used alone or in combination. Among these, aliphatic polyester resins or aliphatic aromatic polyester resins are preferred. Examples of aliphatic polyester resins include aliphatic polyesters obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in mixtures. Of these, 1,4-butanediol is preferred. Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides derived from these may also be used. Among these, succinic acid or succinic anhydride, or a mixture of these with adipic acid, is preferred. Specific examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (e.g., BioPBS manufactured by PPT MCC Biochem), and polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid.

[0138] Aliphatic aromatic polyester resins include copolymers containing aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and linear aliphatic and / or alicyclic diol units. The diol component that provides the diol units typically has 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Among these, diols with 2 to 4 carbon atoms are preferred, with ethylene glycol and 1,4-butanediol being preferred, and 1,4-butanediol being even more preferred. The dicarboxylic acid component that provides the dicarboxylic acid units typically has 2 to 10 carbon atoms, such as succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Of these, succinic acid or adipic acid is preferred. Examples of aromatic dicarboxylic acid components that provide aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.Specific examples include PBAT, which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid (for example, Ecoflex manufactured by BASF Co., Ltd.).

[0139] Other examples include poly(3-hydroxyalkanoates) which are aliphatic polyester copolymers obtained from hydroxyalkanoic acids and polycarboxylic acids (particularly, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., Aonilex manufactured by Kaneka Corporation), and polylactic acid (PLA) (e.g., REVODE manufactured by Kaisei Biomaterials Co., Ltd., and Ingeo manufactured by NatureWorks).

[0140] The biodegradable film may be a laminate of multiple biodegradable films or a laminate of a conventional petroleum-based film and a biodegradable film. These biodegradable films may be unstretched or stretched, and there are no limitations on the manufacturing method.

[0141] The film may be one that has been subjected to a stretching treatment. A typical stretching method involves melt-extruding a resin into a sheet using an extrusion film-forming method or the like, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method that combines longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter is often used.

[0142] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer without defects such as film breakage or repellency is formed.

[0143] Alternatively, a film laminated with a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer of polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. Use of such a film can provide a laminate with barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0144] The paper can be made from any known paper base material without any particular limitations. Specifically, it is produced using natural fibers for papermaking, such as wood pulp, on a known papermaking machine, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp, such as softwood pulp and hardwood pulp; non-wood pulp, such as Manila hemp pulp, sisal hemp pulp, and flax pulp; and pulp obtained by chemically modifying these pulps. Examples of pulp that can be used include chemical pulp produced by sulfate cooking, acidic, neutral, or alkaline sulfite cooking, soda cooking, ground pulp, chemi-ground pulp, and thermomechanical pulp. Various commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, and paperboard can also be used.

[0145] More specific examples of the laminate configuration include, but are not limited to, (1) substrate 1 / adhesive layer 1 / sealant film (2) substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (7) substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (8) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (9) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (10) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film.

[0146] Examples of the substrate 1 used in structure (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, and the like. Furthermore, the substrate 1 may be coated to improve gas barrier properties or ink receptivity when a printing layer (described later) is provided. Commercially available coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-open heat seal film, and gas barrier heat seal film. A printing layer may be provided on the surface of the substrate 1 facing the adhesive layer 1 (when a coated substrate film 1 is used, the surface of the coating layer facing the adhesive layer 1) or on the surface opposite the adhesive layer 1. The printing layer is formed using various printing inks, such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using a common printing method conventionally used for printing on polymer films and paper.

[0147] Examples of the substrate 1 used in structures (2) and (3) include an MDOPE film, an OPE film, an OPP film, a PET film, and paper. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of metal-vapor-deposited unstretched films include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film obtained by vapor-depositing a metal such as aluminum on a gas-barrier heat-sealable film. Examples of metal-vapor-deposited stretched films include a VM-MDOPE film, a VM-OPE film, or a VM-OPP film obtained by vapor-depositing a metal such as aluminum on an MDOPE film, an OPE film, or an OPP film. As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0148] Examples of transparent vapor-deposited stretched films used in structure (4) include films obtained by depositing silica or alumina on MDOPE film, OPE film, OPP film, PET film, nylon film, etc. A film with a coating applied to the inorganic vapor-deposited layer of silica or alumina may also be used for the purpose of protecting the inorganic vapor-deposited layer. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include those similar to those in structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film facing the adhesive layer 1 (when a film with a coating applied to the inorganic vapor-deposited layer is used, the surface of the coating layer facing the adhesive layer 1). The method of forming the printed layer is the same as in structure (1).

[0149] Examples of the substrate 1 used in structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0150] Examples of the substrate 1 in structure (6) include those similar to those in structures (2) and (3). Examples of metal-vapor-deposited stretched films include VM-MDOPE films, VM-OPE films, VM-OPP films, and VM-PET films, which are MDOPE films, OPE films, OPP films, and PET films that have been subjected to metal vapor deposition of aluminum or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0151] Examples of the substrate 1 in structure (7) include PET film, paper, etc. Examples of the transparent vapor-deposited stretched film include those similar to those in structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0152] Examples of the substrate 1 in structure (8) include PET film and paper. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0153] Examples of the substrate 1 in structures (9) and (10) include PET film, paper, etc. Examples of the substrate 2 include nylon film, etc. Examples of the metal layer include aluminum foil, etc. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0154] When the laminate of the present invention includes at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer, the adhesive layer in contact with the metal vapor deposition layer, the transparent vapor deposition layer, and the metal layer is preferably a cured coating film of the adhesive of the present invention.

[0155] When the adhesive of the present invention is used as an adhesion promoter, the adhesion promoter of the present invention is applied to a film material as a substrate using a roll such as a gravure roll, the organic solvent is evaporated by heating in an oven or the like, and then a molten polymer material is laminated using an extruder to obtain the laminate of the present invention.

[0156] The laminate of the present invention may further include other films or substrates in addition to the above-described configurations (1) to (10). As the other substrates, in addition to the above-described stretched films, unstretched films, and transparent vapor-deposited films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used to bond the other substrates may or may not be the adhesive of the present invention.

[0157] The "other layer" may contain known additives or stabilizers, such as antistatic agents, adhesion-enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the "other layer" may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, or the like in order to improve adhesion when laminated with other materials.

[0158] The laminate of the present invention can be suitably used for a variety of applications, such as packaging materials for food, medicines, and daily necessities; lid materials; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; barrier materials; roofing materials; solar cell panel materials; battery packaging materials; window materials; outdoor flooring materials; lighting protection materials; automotive components; signs; stickers and other outdoor industrial applications; decorative sheets used in simultaneous injection molding decoration methods; and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0159] <Packaging Material> The laminate of the present invention can be used as a multilayer packaging material for protecting foods, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the packaging of the present invention may be appropriately provided with an easy-open treatment or a resealable means.

[0160] A specific example of the packaging material of the present invention is a packaging material obtained by forming a bag from a laminate having a sealant film, such as the laminate configuration examples (1), (4), and (10) described above. The laminate is folded or overlapped so that the inner layer surfaces (the surfaces of the sealant film) face each other, and the peripheral edges are heat-sealed to form a bag. Examples of bag-making methods include heat-sealing methods using a side seal, two-sided seal, three-sided seal, four-sided seal, envelope seal, flared seal, flat-bottom seal, square-bottom seal, gusset seal, or other heat seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage pattern. Self-standing packaging materials (standing pouches) are also possible. Examples of heat-sealing methods include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0161] The packaging material of the present invention is filled with contents through its opening, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of contents to be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and processed fish ham and meat products. Examples of such foods include processed seafood products such as sausages, fish paste products, kamaboko, nori seaweed, tsukudani (simmered foods in soy sauce), bonito flakes, salted fish, smoked salmon, and spicy mentaiko; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as frozen and chilled prepared dishes, including hamburgers, meatballs, fried seafood, gyoza, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0162] In addition, the present invention can also be used as a packaging material for various non-food products, such as cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and emulsion, vacuum insulation materials, batteries, etc.

[0163] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0164] Example 1 (Step 1) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser was charged with 835.2 parts of 2,4-toluene diisocyanate and 208.8 parts of 2,6-toluene diisocyanate as the toluene diisocyanate (o), and 134.0 parts of trimethylolpropane as the polyol (p). The mixture was heated to 90°C with stirring under a nitrogen gas stream, and reacted at 90°C for 2 hours to obtain a composition containing polyurethane polyisocyanate (A1) and toluene diisocyanate (o').

[0165] (Step 2) The composition obtained in step 1 was purified using a thin-film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C to remove unreacted toluene diisocyanate (o'). This yielded polyisocyanate composition (X-1). The ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate in the recovered toluene diisocyanate (o') was 7:3.

[0166] (Step 3) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser was charged with 522 parts of the toluene diisocyanate (o') recovered in step 2 as the toluene diisocyanate (q), 417.6 parts of 2,4-toluene diisocyanate, 104.4 parts of 2,6-toluene diisocyanate, and 134.0 parts of trimethylolpropane as the polyol (r), and the mixture was heated to 90°C with stirring under a nitrogen gas stream and reacted at 90°C for 2 hours to obtain a composition containing polyurethane polyisocyanate (A-2) and toluene diisocyanate (q').

[0167] (Step 4) The composition obtained in step 3 was purified using a thin-film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C to remove toluene diisocyanate (q'), thereby obtaining a polyisocyanate composition (X-2).

[0168] The physical properties of the polyisocyanate composition (X-1) and the polyisocyanate composition (X-2) are summarized in Table 1. It was confirmed that the production method of the present invention, even when using toluene diisocyanate recovered from the production process, can produce a polyurethane polyisocyanate that is comparable to that obtained when no toluene diisocyanate recovered from the production process is used.

[0169]

Claims

1. Step 1 of reacting toluene diisocyanate (о) containing 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, in which the proportion of 2,4-toluene diisocyanate is 50% by mass or more and 90% by mass or less, with a polyol (p) under conditions in which the number of isocyanate groups in the toluene diisocyanate (о) is at least twice as many as the number of hydroxyl groups in the polyol (p), to obtain a composition containing a polyurethane polyisocyanate (A1) and toluene diisocyanate (о'); and Step 2 of removing the toluene diisocyanate (о') from the composition obtained in Step 1. The method for producing a polyurethane polyisocyanate includes: a step 3 of reacting toluene diisocyanate (q), which is obtained by adding 2,4-toluene diisocyanate to at least a part of the toluene diisocyanate (о') to adjust the 2,4-toluene diisocyanate content to 50 mass % or more and 90 mass % or less, with a polyol (r) under conditions in which the number of isocyanate groups in the toluene diisocyanate (q) is at least twice as many as the number of hydroxyl groups in the polyol (r), to obtain a composition containing a polyurethane polyisocyanate (A2) and toluene diisocyanate (q'); and a step 4 of removing the toluene diisocyanate (q') from the composition obtained in the step 3.

2. A method for producing a polyurethane polyisocyanate as described in claim 1, wherein the toluene diisocyanate (q) is obtained by adding 2,4-toluene diisocyanate and 2,6-toluene diisocyanate to at least a portion of the toluene diisocyanate (о') so that the 2,4-toluene diisocyanate content is adjusted to 50% by mass or more and 90% by mass or less.

3. A method for producing a polyurethane polyisocyanate according to claim 1, wherein the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) are the same.

4. The method for producing a polyurethane polyisocyanate according to claim 1, wherein the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) are different.

5. A method for producing a polyurethane polyisocyanate according to claim 1, wherein the toluene diisocyanate (o') and the toluene diisocyanate (q') are stored in the same container.

6. A method for producing a polyurethane polyisocyanate according to claim 1, wherein the toluene diisocyanate (o') and the toluene diisocyanate (q') are stored in different containers.

7. A method for producing a polyurethane polyisocyanate as described in claim 1, wherein in step 2, the toluene diisocyanate (о') is removed by passing through a distillation apparatus 1 and a distillation apparatus 2 connected in series, and the toluene diisocyanate (о'-1) recovered from the distillation apparatus 1 and the toluene diisocyanate (о'-2) recovered from the distillation apparatus 2 are stored in the same container.

8. A method for producing a polyurethane polyisocyanate as described in claim 1, wherein in step 2, the toluene diisocyanate (о') is removed by passing through distillation apparatus 1 and distillation apparatus 2 connected in series, and the toluene diisocyanate (о'-1) recovered from the distillation apparatus 1 and the toluene diisocyanate (о'-2) recovered from the distillation apparatus 2 are stored in different containers.

9. A polyisocyanate composition comprising a polyurethane polyisocyanate obtained by the method according to any one of claims 1 to 8.

10. A two-component curing composition comprising the polyisocyanate composition according to claim 9 and an isocyanate-reactive composition.

11. A two-component curing composition comprising the polyisocyanate composition according to claim 9 and a polyol composition.

12. A laminate comprising a first substrate, a second substrate, and an adhesive layer that bonds the first substrate and the second substrate, the adhesive layer being a cured coating film of the two-component curing adhesive described in claim 11.

13. A packaging material comprising the laminate according to claim 12.

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