Urethane resin-forming composition and two-component adhesive

Abstract

To provide a urethane resin forming composition that contributes to producing a urethane resin with excellent toughness and a high Tg.SOLUTION: A urethane resin forming composition includes a component (A) that includes an isocyanate-terminated prepolymer resulting from the reaction of polyisocyanate with a hydroxy group-bearing chlorinated polyolefin, and a component (B) that includes a polyol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a urethane resin-forming composition and a two-component adhesive. [Background technology]

[0002] Various types of adhesives are known, including epoxy adhesives and urethane adhesives. Structural adhesives require strength and durability, and especially in automotive applications, a high glass transition temperature (Tg) is required from the standpoint of strength stability in the operating temperature range. Generally, epoxy adhesives have a higher Tg and higher strength compared to urethane adhesives, but they are brittle.

[0003] For this reason, urethane-based adhesives are attracting attention as structural adhesives where toughness is required. Reactive two-component adhesives are sometimes used as urethane-based adhesives, and such adhesives include, for example, the one disclosed in Patent Document 1. According to the two-component urethane-based adhesive composition of Patent Document 1, it is said that good adhesive performance can be obtained without primer treatment or sanding treatment, while also having excellent storage stability of the first component.

[0004] The composition disclosed in Patent Document 1 consists of a first liquid containing a prepolymer obtained by reacting a polyisocyanate with a polyol, and a second liquid containing a polyol and a catalyst. The first liquid is composed of a prepolymer and filler obtained by reacting a polyisocyanate with a high molecular weight polyol (I) having a number average molecular weight of 1000 or more, and the second liquid contains a high molecular weight polyol (II) having a number average molecular weight of 1000 or more and a low molecular weight polyol having a number average molecular weight of less than 1000, with the molar ratio of (I), (II), and the low molecular weight polyol being predetermined amounts. In Patent Document 1, only polyether polyols are used as both high molecular weight polyols and low molecular weight polyols. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2009 / 047962 [Overview of the project] [Problems that the invention aims to solve]

[0006] While urethane adhesives generally exhibit excellent toughness, it is not easy to increase the Tg while maintaining excellent toughness. If a urethane resin-forming composition can be obtained that forms a cured product exhibiting not only excellent toughness but also a high Tg, the shortcomings of existing high-strength adhesives such as epoxy adhesives will be overcome.

[0007] Therefore, one object of the present invention is to provide a urethane resin-forming composition that contributes to the production of a urethane resin exhibiting excellent toughness and high Tg. Another object of the present invention is to provide a two-component adhesive using such a composition. [Means for solving the problem]

[0008] The present invention provides a urethane resin-forming composition containing component (A), which is an isocyanate-terminated prepolymer that is a reaction product of polyisocyanate and hydroxyl-containing chlorinated polyolefin, and component (B), which is a polyol.

[0009] This urethane resin-forming composition can form a urethane resin having excellent toughness and a high Tg. Here, "resin" refers to the substance formed by the reaction of unreacted components (or, if the composition is used as an adhesive, the cured adhesive). In the context of the present invention, the reaction product (cured product) of component (A) and component (B) corresponds to the resin.

[0010] Component (B) may include a crosslinking agent (b1) and a carbonate group-containing polyol (b2), and the carbonate group-containing polyol (b2) may be liquid at 23°C. By including such components, it becomes possible to form a highly tough and high Tg urethane resin that can be used in a wide temperature range from low to high temperatures. In this invention, "liquid" at 23°C means having fluidity at 23°C. More specifically regarding fluidity, the material is placed in a flat-bottomed cylindrical glass test tube with an inner diameter of 30 mm and a height of 120 mm, with the material filling the tube to a height of 55 mm, the test tube is kept at 23°C, and the test tube is held horizontally. If the leading edge of the liquid surface of the material passes through a point 85 mm from the bottom of the test tube within 90 seconds, it is considered liquid.

[0011] The chlorine content of hydroxyl group-containing chlorinated polyolefins may be 50% or less. By keeping the chlorine content within this range, the Tg does not become too high, and the toughness value can be maintained at a high level. The acetoxy group content of hydroxyl group-containing chlorinated polyolefins may be 10 mmol / g or less. Hydroxyl group-containing chlorinated polyolefins can be synthesized, for example, by introducing hydroxyl groups by transesterifying the acetoxy groups of a chlorinated ethylene-vinyl acetate copolymer. If the acetoxy group content is within the above range, a sufficient amount of hydroxyl groups is introduced, and based on this, the toughness and Tg become sufficiently high.

[0012] The hydroxyl value of hydroxyl-containing chlorinated polyolefins may be 80 KOH mg / g or less. A higher hydroxyl value improves the molar concentration of hydroxyl groups per gram of hydroxyl-containing chlorinated polyolefin. However, simply increasing the molar concentration of hydroxyl groups is not sufficient for high toughness and Tg; optimization is possible by keeping it below the above value.

[0013] Component (A) and / or component (B) may contain an inorganic filler. By including an inorganic filler, the physical properties of the cured product of the urethane resin-forming composition can be appropriately adjusted to suit the actual application.

[0014] In addition to the above urethane resin-forming composition, the present invention provides a two-component adhesive comprising the above urethane resin-forming composition.

Advantages of the Invention

[0015] According to the present invention, a urethane resin-forming composition is provided that contributes to the production of a urethane resin exhibiting excellent toughness and a high Tg. Further, a two-component adhesive using this composition is provided.

Modes for Carrying Out the Invention

[0016] Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail.

[0017] The urethane resin-forming composition according to the embodiment contains a component (A) containing an isocyanate-terminated prepolymer which is a reaction product of a polyisocyanate and a hydroxyl group-containing chlorinated polyolefin (hereinafter sometimes simply referred to as "isocyanate-terminated prepolymer"), and a component (B) containing a polyol.

[0018] Component (A) only needs to contain an isocyanate-terminated prepolymer, and may contain, in addition to the isocyanate-terminated prepolymer, a filler, polymer particles, an antioxidant, a stabilizer, etc. The isocyanate-terminated prepolymer is also preferably liquid at room temperature (23°C). Liquid means as defined above, and it only needs to be mixable with component (B).

[0019] The polyisocyanate constituting the isocyanate-terminated prepolymer may be any compound containing two or more isocyanate groups in the molecule. The polyisocyanate may be partially trimerized using a trimerization catalyst or partially allophanatized using an allophanatization catalyst. In addition, it may be prepolymerized using a polyol or the like as a modifier.

[0020] Examples of polyisocyanates that constitute isocyanate-terminated prepolymers include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and aromatic aliphatic isocyanates.

[0021] Aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ether diiso Examples include cyanates, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

[0022] Aliphatic isocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Examples include isocyanates, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate 4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate 5-isocyanate methyl octane, bis(isocyanate ethyl) carbonate, bis(isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanate methyl ester, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and 2-isocyanate propyl-2,6-diisocyanate hexanoate.

[0023] Alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanate methyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate n-butylidene)pentaerythritol, hydrogenated hydrogenated dimer acid diisocyanate, and 2-isocyanate. Isocyanatemethyl-3-(3-isocyanatetopropyl)-5-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatetopropyl)-6-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatetopropyl)-5-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatetopropyl)-6-isocyanatemethyl -Bicyclo[2.2.1]-heptane,2-isocyanatemethyl-3-(3-isocyanatetopropyl)-5-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane,2-isocyanatemethyl-3-(3-isocyanatetopropyl)-6-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane,2-isocyanatemethyl-2-(3-isocyanatetopropyl)-5-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane,2- Examples include socyanatemethyl-2-(3-isocyanatetopropyl)-6-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane, 2,5-bis(isocyanatemethyl)-bicyclo[2.2.1]-heptane, hydrogenated hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated hydrogenated tolylene diisocyanate, hydrogenated hydrogenated xylene diisocyanate, and hydrogenated hydrogenated tetramethylxylene diisocyanate.

[0024] Examples of aromatic aliphatic isocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

[0025] The hydroxyl group-containing chlorinated polyolefin constituting the isocyanate-terminated prepolymer is not particularly limited. Examples of synthesis methods include de-esterification of a chlorinated ethylene-vinyl acetate copolymer by transesterification with alcohol under acidic or basic conditions, or chlorination of a saponified ethylene-vinyl acetate copolymer. Among these, the method utilizing transesterification of a chlorinated ethylene-vinyl acetate copolymer with alcohol under acidic conditions is preferred because it requires a short reaction time.

[0026] The above-mentioned chlorinated ethylene-vinyl acetate copolymer can be synthesized by conventionally known methods. For example, it can be synthesized by dissolving it in a chlorine-based solvent such as carbon tetrachloride, chloroform, or 1,1,2-trichloroethane, and then blowing in chlorine gas in the presence of a radical initiator. The reaction temperature is not particularly limited, but is between 60 and 180°C, and the reaction pressure is not particularly limited, but atmospheric pressure to 1.0 megapascal is appropriate.

[0027] After the chlorination reaction is complete, any remaining chlorine gas and by-product hydrogen chloride gas in the solution are removed from the reaction system by blowing in an inert gas such as nitrogen under reflux of the solvent. The resulting chlorinated ethylene-vinyl acetate copolymer is separated from the solvent by steam distillation, drum drying, extrusion drying, or other methods as needed.

[0028] The following describes a method for synthesizing hydroxyl group-containing chlorinated polyolefins using the transesterification reaction of chlorinated ethylene-vinyl acetate copolymers with alcohol under acidic conditions.

[0029] After dissolving the chlorinated ethylene-vinyl acetate copolymer in a solvent, an acid and an alcohol are added. The reaction temperature is not particularly limited, but is 10 to 100°C. Examples of solvents for dissolving the chlorinated ethylene-vinyl acetate copolymer include halogenated organic solvents such as chloroform, methylene chloride, and 1,1,2-trichloroethane, and aromatic organic solvents such as benzene, toluene, and xylene. Any acid that dissolves in the mixture of the solvent and alcohol can be used in the reaction, such as hydrogen chloride, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Hydrogen chloride is preferred because it is easy to remove after the reaction. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, and n-butanol. Primary alcohols are preferred because they have a fast reaction rate. Alcohols with 4 or fewer carbon atoms are also preferred because they are easy to remove. Methanol is particularly preferred because it has a fast reaction rate and is easy to remove. Methods for separating the polymer from the reaction solution after the reaction is complete include, for example, removing the solvent under reduced pressure, removing the solvent using a drum dryer, and reprecipitation by adding the reaction solution to a poor solvent such as methanol to isolate the polymer.

[0030] Hydroxyl group-containing chlorinated polyolefins have repeating units represented, for example, -(CH2-CH2)-, -(CH2-CHCl)-, -(CH2-CHOH)-, and -(CH2-CHOAc)-, where OAc represents an acetoxy group. That is, hydroxyl group-containing chlorinated polyolefins may have acetoxy groups in addition to hydroxyl groups and chlorine atoms. The acetoxy group content is preferably 10 mmol / g or less (0 to 10 mmol / g), and may be 0.01 to 0.8 mmol / g, 0.01 to 0.7 mmol / g, 0.01 to 0.6 mmol / g, 0.02 to 0.6 mmol / g, or 0.03 to 0.6 mmol / g.

[0031] The molecular weight of the hydroxyl group-containing chlorinated polyolefin may be 60,000 g / mol or less, and may be 3,000 to 50,000 g / mol, 5,000 to 40,000 g / mol, 6,000 to 40,000 g / mol, 8,000 to 40,000 g / mol, or 8,500 to 35,000 g / mol. By setting the molecular weight to 60,000 g / mol or less, compounding is facilitated when reacting with component (B) to form a urethane resin. The molecular weight of the hydroxyl group-containing chlorinated polyolefin can further be 5,000 to 38,000 g / mol or 9,000 to 35,000 g / mol. This results in improved toughness and Tg.

[0032] The chlorine concentration of the hydroxyl group-containing chlorinated polyolefin may be 55% or less, 52% or less, or 50% or less. The chlorine concentration of the hydroxyl group-containing chlorinated polyolefin can also be 10-55%, 10-52%, 10-50%, 20-55%, 20-52%, 20-50%, 30-55%, 30-52%, or 30-50%. When the chlorine concentration is within the above range (especially 50% or less), the Tg of the hydroxyl group-containing chlorinated polyolefin does not become too high, and the effect of improving fracture toughness is further enhanced. The chlorine concentration of the hydroxyl group-containing chlorinated polyolefin can also be further set to 31-44% or 32-41%. This results in better toughness and Tg.

[0033] The hydroxyl value of hydroxyl-containing chlorinated polyolefins may be 80 KOH mmol / g or less, or 70 KOH mmol / g or less. A hydroxyl value of 80 KOH mmol / g or less enhances the effect of improving fracture toughness. The hydroxyl value of hydroxyl-containing chlorinated polyolefins can also be set to 15-80 KOH mmol / g or 20-64 KOH mmol / g. This results in improved toughness and Tg (transition time).

[0034] In the terminal isocyanate of the isocyanate-terminated prepolymer, it is preferable that the proportion of isocyanate groups derived from 2,4'-diphenylmethane diisocyanate is 30% by mass or more. The proportion of isocyanate groups derived from 2,4'-diphenylmethane diisocyanate may be 30-60% by mass, 40-60% by mass, or 50-60% by mass. By using a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate as the polyisocyanate used to obtain the isocyanate-terminated prepolymer, and by making the proportion of 2,4'-diphenylmethane diisocyanate in this mixture 30% by mass or more, it becomes easy to make the proportion of isocyanate groups derived from 2,4'-diphenylmethane diisocyanate in the terminal isocyanate 30% by mass or more. A preferred mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate is Millionate NM (4,4'-diphenylmethane diisocyanate / 2,4'-diphenylmethane diisocyanate = 45 / 55) manufactured by Tosoh Corporation.

[0035] Furthermore, the isocyanate-terminated prepolymer is preferably liquid at 23°C. Here, the definition of liquid is as described above.

[0036] Component (B) contains a polyol and may contain a crosslinking agent (b1) and a carbonate group-containing polyol (b2). The crosslinking agent (b1) is a compound that reacts with the isocyanate-terminated prepolymer of component (A) to introduce a crosslinked structure, and a crosslinking agent with an average of 3 or more functional groups is preferred. Component (B) may also contain reaction inhibitors, antioxidants, defoamers, etc. These may be added to component (A) instead of component (B), or to both component (A) and component (B).

[0037] The total content of the crosslinking agent (b1) and the carbonate group-containing polyol (b2) relative to the total amount of component (B) can be, for example, 80-100% by mass, 85-100% by mass, 90-100% by mass, 95-100% by mass, or 100% by mass.

[0038] Examples of crosslinking agents (b1) include polyols with an average number of 3 or more functional groups, such as glycerin, trimethylolpropane, pentaerythritol, N,N-bishydroxypropyl-N-hydroxyethylamine, triethanolamine, triisopropanolamine, monomer polyols of ethylenediamine propylene oxide modified, monomer polyols of trimethylolpropane propylene oxide modified, and pentaerythritol propylene oxide modified; as well as polycaprolactone polyols obtained by ring-opening addition of cyclic esters such as ε-caprolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, and δ-valerolactone to polyols such as glycerin, trimethylolpropane, and pentaerythritol as initiators; and the like. These may be used individually or in combination of two or more. Furthermore, if the carbonate group-containing polyol is a polyol with an average number of functional groups exceeding 2, then the polyol shall be included in the carbonate group-containing polyol (b2) rather than the crosslinking agent (b1).

[0039] The carbonate group-containing polyol (b2) is used from the viewpoint of strength, heat resistance, weather resistance, and durability, and when considering its use as an adhesive, liquid polycarbonate polyol that can be handled in liquid form at room temperature (23°C) is particularly preferred.

[0040] Examples of carbonate group-containing polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, and dimethylol. Examples include those obtained from de-alcoholization or de-phenolization reactions of one or more polyols such as acid diols, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol; and one or more dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, and carbonates such as diphenyl carbonate, dinaphthyl carbonate, diantryl carbonate, diphenanthryl carbonate, and diindanyl carbonate. These may contain one or more of these substances.

[0041] The urethane resin-forming composition may contain a solvent. That is, at least one of component (A) and component (B) may contain a solvent. Preferably, the total solvent content is 1% by mass or less, and it is particularly preferable that the composition is substantially solvent-free. A substantially solvent-free composition includes cases where solvent components are present as impurities, or where an amount of solvent components that cannot be removed by purification is present. When the solvent content in the composition is 1% by mass or less, it is possible to further suppress the occurrence of dripping due to excessively low viscosity.

[0042] A catalyst may also be used to promote the reaction between the isocyanate-terminated prepolymer and the polyol. That is, at least one of component (A) and component (B) may contain a catalyst. From the viewpoint of controlling reactivity, the catalyst content is particularly preferable to be 0.05% by mass or less based on the total amount of the composition. Examples of catalysts include isocyanurate catalysts and urethane catalysts, and specific examples are shown below.

[0043] Examples of isocyanurate catalysts include triethylamine, N-ethylpiperidine, N,N'-dimethylpiperazine, N-ethylmorpholine, tertiary amines such as Mannich bases of phenolic compounds, and potassium acetate. These isocyanurate catalysts can be used individually or in combination of two or more.

[0044] As the urethane catalyst, it can be appropriately selected from known catalysts, and examples include amine-based catalysts, imidasol-based catalysts, and metal catalyst systems.

[0045] Examples of amine catalysts include triethylenediamine, 2-methyltriethylenediamine, 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, and bis(2-dimethylaminoethyl) ether.

[0046] Examples of imidazole-based catalysts include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole.

[0047] Examples of metal catalysts include organotin catalysts such as stanus diacetate, stanus dioctoate, stanus dioleate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate.

[0048] The urethane resin formed from the compositions of the above embodiments exhibits excellent fracture toughness. The fracture toughness was evaluated by a DCB test, which was conducted in accordance with ASTM D3433-99.

[0049] The urethane resin-forming composition can also be used as an adhesive for various applications (especially two-component adhesives), and its application fields include, for example, the automotive, display, recording medium, electronic materials, battery, optical components, construction, electronic equipment, and aerospace industries.

[0050] In the automotive sector, for example, it can be used in structural parts, switches, headlamps, engine components, electrical components, drive engines, and brake fluid tanks. In the display sector, for example, it can be used in liquid crystal displays, organic electroluminescent displays, and light-emitting diode displays. In the recording medium sector, for example, it can be used in video discs, CDs, DVDs, MDs, pickup lenses, VCM magnets, spindle motors, hard disk peripheral components, and Blu-ray discs.

[0051] In the field of electronic materials, for example, it can be used in electronic components, electrical circuits, electrical contacts, or semiconductor devices. More specifically, these applications include encapsulating materials, die bonding agents, conductive adhesives, anisotropic conductive adhesives, and interlayer adhesives for multilayer substrates, including build-up substrates. In the field of batteries, for example, it can be used in lithium-ion batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, and organic solar cells. In the field of optical components, for example, it can be used in optical fiber materials around optical switches and optical connectors in optical communication systems, as well as in optical passive components, optical circuit components, and around optoelectronic integrated circuits. In the field of electronic equipment, for example, it can be used in camera modules.

[0052] The urethane resin-forming composition is used by mixing component (A) and component (B) and reacting them. After mixing, it may be stored at room temperature (23°C) to cure, or it may be heated and cured at, for example, 80-180°C for 1-60 minutes. [Examples]

[0053] The present invention will be described in more detail below based on the following examples, but the present invention is not limited to the following examples.

[0054] The values ​​used in these examples were obtained in accordance with the following measurement methods.

[0055] [Chlorine content] The chlorine content of hydroxyl-containing chlorinated polyolefins was measured using the combustion flask method. To measure the chlorine content, approximately 20 mg of hydroxyl-containing chlorinated polyolefin was combusted according to the oxygen flask combustion method, and 15 mL of 1.7 wt% hydrazinium sulfate aqueous solution was allowed to stand as the absorption solution. After 40 minutes, the absorption solution was washed with approximately 100 mL of pure water, and the chloride ions were quantified by potentiometric titration using a 0.5 N silver nitrate aqueous solution with an automatic titrator (Hiruma Sangyo Co., Ltd., MC-3000, TS-3000) to determine the chlorine content.

[0056] [Acetoxy group content] The acetoxy group content of the hydroxyl group-containing chlorinated polyolefin and the chlorinated ethylene-vinyl acetate copolymer was , measured by ¹H-NMR. Approximately 100 mg (W P ) of the hydroxyl group-containing chlorinated polyolefin or the chlorinated ethylene-vinyl acetate copolymer was dissolved in approximately 1 mL of deuterated chloroform, and approximately 8.8 mg (W B ) of benzene was added as an internal standard substance, and ¹H-NMR analysis was performed using an NMR (JNM-ECZ400S / L1 manufactured by JEOL Ltd.) at 400 Hz. 1 From the obtained 1 ¹H-NMR chart, the integrated values (S B , S Ac [[ID=十七]]) of benzene (7.35 ppm) and CH-OAc (4.73 to 5.47 ppm) were calculated, and the acetoxy group content was calculated from Equation (1). Acetoxy group content (mmol / g) = W B × S Ac × 10 3 / (W P × S B × 78.11 / 6) ··· (1)

[0057] [Hydroxyl group content (hydroxyl value)] 1 Using the acetoxy group content (Ac SM , Ac RM ) of each of the hydroxyl group-containing chlorinated polyolefin and the chlorinated ethylene-vinyl acetate copolymer used as its raw material, which were measured by ¹H-NMR, the hydroxyl group amount was calculated from Equation (2). Hydroxyl group content (mmol / g) = [Ac SM / (100 - 42.04 × Ac SM / 1000)] - [Ac SM / (100 - 42.04 × Ac SM / 1000)] × Ac RM / Ac SM ··· (2) Using the hydroxyl group content (mmol / g) calculated by Equation (2), the hydroxyl value was calculated from Equation (3). Hydroxyl value (KOHmg / g) = Hydroxyl group content (mmol / g) × 56.11 ··· (3)

[0058] [Measurement of solid content in chlorination reaction solution] 1-2 g of the chlorinated reaction solution was dried at 100°C for 10 minutes and then at 140°C for 40 minutes, and the solid content was calculated from the weight change before and after drying.

[0059] [Measurement of molecular weight] The molecular weight of the polymer solution obtained by dissolving 10 mg of hydroxyl-containing chlorinated polyolefin in 10 mL of THF was measured by GPC. The weight-average molecular weight (Mw) was determined using standard polystyrene (manufactured by Tosoh Corporation) and converted to polystyrene equivalent. The measurement conditions are shown below. • Model: (Product Name) HLC8420GPC • Solvent: THF Column temperature: 40°C ·Measurement concentration: 10mg / 10mL ·Injection volume: 200μL • Column: TSKgel G7000HXL (manufactured by Tosoh Corporation) → TSKgel GMHXL (manufactured by Tosoh Corporation) 2 pieces

[0060] [Measurement of glass transition temperature] The glass transition temperature (Tg) was defined as the starting point of the transition region in the DSC curve measured using a differential scanning calorimetry analyzer (NETZSCH, DSC3500 Sirius) under nitrogen vapor flow, with the temperature increased from -100°C to 150°C at a rate of 10°C / min.

[0061] A hydroxyl group-containing chlorinated polyolefin having repeating units represented by -(CH2-CH2)-, -(CH2-CHCl)-, -(CH2-CHOH)-, and -(CH2-CHOAc)- was produced by the transesterification reaction of a chlorinated ethylene-vinyl acetate copolymer.

[0062] A chlorinated ethylene-vinyl acetate copolymer was produced by the method described below. The raw materials used are as follows:

[0063] [Raw materials] • U530: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: Ultrasen 530, vinyl acetate content: 6% by weight, melt mass flow rate (JIS K 6924-1): 75g / 10 min) • U685: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: Ultrasen 685, vinyl acetate content: 14% by weight, melt mass flow rate (JIS K 6924-1): 2500g / 10 min) • U520F: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: Ultrasen 520F, vinyl acetate content: 8% by weight, melt mass flow rate (JIS K 6924-1): 2g / 10 min) • U680: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: Ultrasen 680, vinyl acetate content: 20% by weight, melt mass flow rate (JIS K 6924-1): 160g / 10 min) • U539: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: UltraCen 539, vinyl acetate content: 6% by weight, melt mass flow rate (JIS K 6924-1): 27.5g / 10 min) • VW331V: Ethylene-vinyl acetate copolymer (manufactured by Innospec, product name: VISCOWAX331V, vinyl acetate content: 11% by weight, viscosity @ 140℃: 65 mm) 2 / s) • U684: Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name: UltraCen 684, vinyl acetate content: 20% by weight, melt mass flow rate (JIS K 6924-1): 2000g / 10 min) • AC 400: Ethylene-vinyl acetate copolymer (manufactured by Honeywell, product name: AC 400, vinyl acetate content: 13% by weight, viscosity @ 140℃: 595 cps) • 1,1,2-Trichloroethane: Manufactured by Tosoh Corporation • α,α'-Azobisisobutyronitrile: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0064] [Production of chlorinated ethylene-vinyl acetate copolymer] Under a nitrogen atmosphere, ethylene-vinyl acetate copolymer and 1,1,2-trichloroethane were added to a 500 mL glass autoclave according to Table 1 and dissolved at 110°C. To this polymer solution, a 0.5 g / L solution of α,α'-azobisisobutyronitrile in 1,1,2-trichloroethane was added dropwise at a rate of 0.1 mL / min while chlorine gas was added at a rate of 100 N mL / min under 110°C conditions, adjusting the pressure to 0.1 MPaG. After adding chlorine gas for the specified time according to Table 1, the temperature and pressure were reduced, and nitrogen gas was introduced at a rate of 150 mL / min for 1 hour at 80°C and atmospheric pressure to obtain a chlorinated ethylene-vinyl acetate copolymer in 1,1,2-trichloroethane. This reaction solution was used directly in the transesterification reaction.

[0065] [Table 1]

[0066] Hydroxyl group-containing chlorinated polyolefins were produced by the following two methods. The raw materials used are as follows. [Raw materials] • Concentrated sulfuric acid: 95%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Concentrated hydrochloric acid: 35%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • 5% hydrogen chloride / methanol solution: Manufactured by Tokyo Chemical Industry Co., Ltd. • 20% hydrogen chloride / methanol solution: Prepared by the method shown below.

[0067] [Preparation of a 20% hydrogen chloride / methanol solution] 171 g of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 500 mL three-necked flask, and the flask was purged with nitrogen. 346 g of concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 95%) was placed in a separately prepared 500 mL three-necked flask, and 123 g of concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 35%) was added dropwise. The generated hydrogen chloride gas was washed with concentrated sulfuric acid and then introduced into the methanol. The introduction of hydrogen chloride gas was carried out for 7 hours. The resulting hydrogen chloride methanol solution was used in the transesterification reaction.

[0068] [Production of hydroxyl group-containing chlorinated polyolefin 1] Synthesis Examples 1, 7, 8, and 10 were produced using the methods described below to manufacture hydroxyl group-containing chlorinated polyolefins.

[0069] A 1,1,2-trichloroethane solution of chlorinated ethylene-vinyl acetate copolymer was placed in a 1 L separable flask and diluted with 1,1,2-trichloroethane to a polymer concentration of 10% by mass. Methanol was added to this polymer solution according to Table 2, and the temperature was raised to 65°C. 123 g of concentrated sulfuric acid was placed in a separately prepared 300 mL three-necked flask, and 44 g of concentrated hydrochloric acid was added dropwise. The generated hydrogen chloride gas was washed with concentrated sulfuric acid and then introduced into the reaction solution containing the dissolved chlorinated ethylene-vinyl acetate copolymer. The introduction of hydrogen chloride gas was carried out for 3 hours, followed by a further 1 hour of reaction, after which nitrogen gas was introduced at a rate of 0.1-0.2 L / min for 1 hour. The solvent was removed from the resulting reaction solution using an evaporator, and then the solution was dried in a vacuum dryer to obtain a hydroxyl group-containing chlorinated polyolefin.

[0070] [Table 2]

[0071] [Production of hydroxyl group-containing chlorinated polyolefins 2] Synthesis Examples 2, 3, 4, 5, 6, 9, 11, and 13 produced hydroxyl group-containing chlorinated polyolefins using the method described below.

[0072] A 1,1,2-trichloroethane solution of chlorinated ethylene-vinyl acetate copolymer was placed in a separable flask and diluted with 1,1,2-trichloroethane to a polymer concentration of 10% by mass. Hydrogen chloride / methanol solution and methanol were added to this reaction mixture according to Table 3, and the mixture was stirred for the reaction time indicated in Table 3. Then, nitrogen gas was introduced at a rate of 0.1 to 0.2 L / min for 1 hour. The solvent was removed from the resulting reaction mixture using an evaporator, and the mixture was dried in a vacuum dryer to obtain a hydroxyl group-containing chlorinated polyolefin.

[0073] [Table 3]

[0074] Isocyanate-terminated polyisocyanates and polyols were produced by the method described below. The raw materials used and their abbreviations are as follows.

[0075] [Raw materials] (1) Component (A) • "NM"; Millionate NM (manufactured by Tosoh Corporation) 4,4'-Diphenylmethane diisocyanate / 2,4'-Diphenylmethane diisocyanate mixture, NCO content=33.5%, f=2 4,4'-Diphenylmethanediisocyanate / 2,4'-Diphenylmethanediisocyanate = 45 / 55 (typical value)

[0076] (2) Component (B) • "PCD1000"; KurarayPolyol C-1090 (manufactured by Kuraray Co., Ltd.), polycarbonate polyol, hydroxyl value = 112KOH mg / g, number of functional groups (f) = 2 • "MA-170"; Leocon MA-170 (manufactured by Lion Specialty Chemicals), N,N-bishydroxypropyl-N-hydroxyethylamine, Hydroxyl value = 950 KOH mg / g, f = 3

[0077] (3) Inorganic fillers • "Zeolite"; Zeoram A-3 (manufactured by Tosoh Corporation) • "Talc"; Crown Talc® (manufactured by Matsumura Sangyo Co., Ltd.)

[0078] [Manufacturing of isocyanate-terminated prepolymers] In a 5 L stirring vessel filled with nitrogen, hydroxyl-containing chlorinated polyolefin was added according to Table 4. The solvent (methyl ethyl ketone) was diluted to a solid content (hydroxyl-containing chlorinated polyolefin + myrionate NM) of 30% by mass. After confirming that the hydroxyl-containing chlorinated polyolefin had dissolved in the solvent, myrionate NM (2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture) was added according to Table 4, and the synthesis was carried out at a liquid temperature of 60°C. The synthesis time was adjusted as appropriate, but in this synthesis, after intermittent synthesis for 24 hours, the solvent was removed using a rotary evaporator to obtain a substantially solvent-free isocyanate-terminated polyisocyanate. In Table 4, "2,4'-amount" refers to the amount (by mass) of 2,4'-diphenylmethane diisocyanate in the isocyanate end.

[0079] [Production of polyols] According to the mixing ratios listed in the "Component (B)" column of Table 4, each material was placed in a nitrogen-filled stirring vessel and stirred. Then, while maintaining the temperature inside the stirring vessel at 40-70°C, the mixture was stirred for 1-3 hours to obtain polyol (Component (B)).

[0080] [Filler composition] According to the mixing ratios listed in "Additives" in Table 4, a mixture of talc and zeolite was added to each of the isocyanate-terminated prepolymer (component (A)) and polyol (component (B)) beforehand. Then, the isocyanate-terminated prepolymer and polyol were mixed using a rotary-rotating agitator (product name: Kakuhunter, manufactured by Shashin Kagaku Co., Ltd.).

[0081] [Composition] Compositions were prepared by combining isocyanate-terminated prepolymers and polyols, each containing a pre-mixed filler, in the proportions listed in the "Formulation" section of Table 4. Then, cured specimens were prepared according to the "Preparation and Evaluation Criteria" described below, and the fracture toughness values ​​were measured using the method described below. The results are shown in Table 4.

[0082] [Test specimen preparation and evaluation criteria] (1) Evaluation of fracture toughness Test specimens were evaluated after being coated with resin, stored at 23°C for 16 hours, baked at 180°C for 20 minutes, and then cured at 23°C for at least 5 hours. Fracture toughness was evaluated by DCB testing in accordance with ASTM D3433-99. The resin thickness was adjusted to 0.35mm using spacers. Spacers use Teflon® tape. Specimen shape: Contoured type used Test substrate: S50C steel (electroless nickel plating treatment) was used. Test conditions: Tensile pressure of 2 mm / min was applied, and the fracture toughness value G was determined based on the maximum load. 1c Calculate Calculation formula: G 1c =[4L 2 (max)](m) / [EB 2 ] L(max) Load:(N) E. Young's modulus of the substrate (MPa): 208000 B. Width of base material (mm): 25.4 m constant (from contoured type): 3.54

[0083] (2) Tg evaluation Dynamic viscoelasticity measurements were performed on 2 mm thick resin sheets prepared by mixing the composition, storing at 23°C for 16 hours, baking at 180°C for 20 minutes, and curing at 23°C for 1 week. The viscoelasticity was measured by temperature dispersion using a viscoelasticity analyzer (product name: DMA7100, manufactured by Hitachi High-Tech Science). The measurement temperature range was -100°C to 250°C, the heating rate was 2 mm / min, and the measurement frequency was 10 Hz. The peak temperature of tanδ was defined as Tg.

[0084] [Table 4]

[0085] The evaluation criteria for fracture toughness and Tg are as shown in Table 5, and the sum of both scores was used as a balance index between fracture toughness and Tg for the overall evaluation. The judgment criteria were as follows: 5 = A (Excellent), 4 = B (Good), 3 = C (Acceptable), 2 or less = D (Poor)

[0086] For flowability, the material was placed in a flat-bottomed cylindrical glass test tube with an inner diameter of 30 mm and a height of 120 mm, with the material height being 55 mm. The test tube was kept at 23°C, the test tube was held horizontally, and a score of "○" was given if the leading edge of the liquid surface of the material passed through a point 85 mm from the bottom of the test tube within 90 seconds.

[0087] [Table 5]

[0088] Examples 1-13 contained hydroxyl group-containing chlorinated polyolefins, with fracture toughness values ​​of 0.7-1.2 kJ / m². 2 The results were good. Furthermore, Examples 1-5 and 11 showed an excellent balance between fracture toughness and Tg. Comparative Example 1 had a good Tg, but did not contain hydroxyl group-containing chlorinated polyolefin, and its fracture toughness value was 0.6 kJ / m 2 Overall, the performance was poor.

Claims

1. Component (A) includes an isocyanate-terminated prepolymer, which is a reaction product of polyisocyanate and hydroxyl-containing chlorinated polyolefin, It contains a polyol-containing component (B), The aforementioned component (B) comprises a crosslinking agent (b1) and a carbonate group-containing polyol (b2), The crosslinking agent (b1) is a urethane resin-forming composition that is not a carbonate group-containing polyol with an average number of functional groups exceeding 2.

2. The composition according to claim 1, wherein the carbonate group-containing polyol (b2) is liquid at 23°C.

3. The composition according to claim 1 or 2, wherein the proportion of isocyanate groups derived from 2,4'-diphenylmethanediisocyanate in the terminal isocyanate of the isocyanate-terminated prepolymer is 30% by mass or more.

4. The composition according to any one of claims 1 to 3, wherein the isocyanate-terminated prepolymer is liquid at 23°C.

5. The composition according to any one of claims 1 to 4, wherein the chlorine content of the hydroxyl group-containing chlorinated polyolefin is 50% or less.

6. The composition according to any one of claims 1 to 5, wherein the acetoxy group content of the hydroxyl group-containing chlorinated polyolefin is 10 mmol / g or less.

7. The composition according to any one of claims 1 to 6, wherein the hydroxyl value of the hydroxyl group-containing chlorinated polyolefin is 80 KOH mg / g or less.

8. The composition according to any one of claims 1 to 7, wherein component (A) and / or component (B) comprises an inorganic filler.

9. A two-component adhesive comprising the composition described in any one of claims 1 to 8.

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