Binder, cured body, and method for producing cured body

Abstract

A binder comprising: a carboxyl group-containing polymer having a weight average molecular weight of 2000 g / mole to 6000 g / mole and a polyol, a molar ratio of carboxylic acid groups of the carboxyl group-containing polymer to the polyol being 79:21 to 35:65, the polyol including a polyol having a viscosity of 900 mPa-s or less at 20°C.

Description

Technical Field

[0001] This disclosure relates to adhesives, cured bodies, and methods for manufacturing cured bodies. Background Technology

[0002] Heat-resistant molded bodies, formed by attaching adhesives to fillers such as glass fibers and shaping them into cushion-like structures, are widely used as insulation materials for residences, warehouses, installations, and equipment. Phenol-formaldehyde adhesives are widely used as these adhesives. However, phenol-formaldehyde adhesives have the problem of unreacted formaldehyde remaining in the molded body and releasing formaldehyde after construction in residences, etc. Therefore, adhesives that do not release formaldehyde are being researched.

[0003] For example, in Patent Documents 1 to 3, adhesives that do not release formaldehyde were proposed as adhesives that are cured by reacting carboxyl-containing polymers such as polyacrylic acid polymers with hydroxyl groups present in themselves or in polyols such as those used as crosslinking agents.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-44253

[0007] Patent Document 2: Japanese Patent Application Publication No. 2016-98285

[0008] Patent Document 3: Japanese Patent Application Publication No. 6-184285 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] Here, the inventors conducted in-depth research and found that conventional binders still have room for improvement in their impregnation of filler materials. Improving the impregnation of the binder is expected to enhance its workability in manufacturing heat-resistant molded articles and suppress deviations in product performance caused by insufficient impregnation. However, when the impregnation of the binder is improved, there is a tendency for a decrease in product strength, making it difficult to improve the binder's impregnation while maintaining product strength.

[0011] Therefore, the purpose of this disclosure is to provide an adhesive that achieves sufficiently high strength and excellent impregnation. Furthermore, the purpose of this disclosure is to provide a cured body using this adhesive and a method for manufacturing the cured body.

[0012] Methods for solving problems

[0013] The binder disclosed herein comprises: a carboxyl-containing polymer having a weight-average molecular weight of 2000 g / mol to 6000 g / mol and a polyol, wherein the molar ratio of the carboxyl groups of the carboxyl-containing polymer to the polyol is 79:21 to 35:65, and the polyol comprises a polyol having a viscosity of less than 900 mPa·s at 20°C.

[0014] In addition, the adhesive of this disclosure comprises a carboxyl-containing polymer and a polyol having a weight-average molecular weight of 2000 g / mol to 6000 g / mol, wherein the molar ratio of the carboxyl group of the carboxyl-containing polymer to the polyol is 79:21 to 35:65, and the polyol may comprise at least one compound selected from the group consisting of hydrocarbon compounds substituted with 2 to 10 hydroxyl groups and polyalkylene glycols.

[0015] The aforementioned hydroxyl-substituted hydrocarbon compound is preferably selected from at least one of the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, erythritol, xylitol, and sorbitol.

[0016] The aforementioned carboxyl-containing polymer preferably contains phosphorus.

[0017] The aforementioned carboxyl-containing polymers preferably contain residues derived from phosphorus-containing oxyacids.

[0018] The aforementioned adhesive preferably also contains polyamines.

[0019] The aforementioned adhesive preferably further comprises a silane coupling agent.

[0020] The aforementioned adhesive preferably further comprises polyamines and silane coupling agents.

[0021] The above-mentioned adhesive preferably has a viscosity of less than 200 mPa·s at 25°C.

[0022] The above-mentioned adhesive can be a fiber adhesive.

[0023] The cured body of this disclosure comprises a cured product of the aforementioned adhesive and a filler material bonded by the cured product. Furthermore, the cured body of this disclosure is formed by curing a precursor comprising a filler material and a carboxyl-containing polymer and a polyol having a weight-average molecular weight of 2000 g / mol to 6000 g / mol in contact with the filler material, wherein the molar ratio of carboxylic acid groups in the carboxyl-containing polymer to the polyol in the precursor is 79:21 to 35:65, and the polyol satisfies at least one of the conditions (1) and (2) below.

[0024] (1) The above polyols include polyols with a viscosity of less than 900 mPa·s at 20°C.

[0025] (2) The above polyols include at least one compound selected from the group consisting of hydrocarbon compounds substituted with 2 to 10 hydroxyl groups and polyalkylene glycols.

[0026] The method for manufacturing the cured body of this disclosure includes: a step of contacting a carboxyl-containing polymer and a polyol having a weight-average molecular weight of 2000 g / mol to 6000 g / mol with a filler material to obtain a precursor, wherein the molar ratio of the carboxyl groups in the carboxyl-containing polymer to the polyol in the precursor is 79:21 to 35:65; and a step of curing the precursor, wherein the polyol satisfies at least one of the conditions (1) and (2) below.

[0027] (1) The above polyols include polyols with a viscosity of less than 900 mPa·s at 20°C.

[0028] (2) The above polyols include at least one compound selected from the group consisting of hydrocarbon compounds substituted with 2 to 10 hydroxyl groups and polyalkylene glycols.

[0029] Invention Effects

[0030] According to this disclosure, an adhesive capable of achieving sufficiently high strength and excellent impregnation can be provided. Furthermore, according to this disclosure, a cured body using the adhesive and a method for manufacturing the cured body can also be provided. Detailed Implementation

[0031] The following describes one embodiment of the present disclosure in detail, but the present disclosure is not limited thereto. It should be noted that in this specification, "(meth)acrylate" refers to "acrylate" or "methacrylate". The same applies to other similar expressions such as "(meth)acrylic acid".

[0032] The adhesive involved in this embodiment comprises a carboxyl-containing polymer (hereinafter also referred to as component (A)) having a weight-average molecular weight of 2000 g / mol to 6000 g / mol and a polyol (hereinafter also referred to as component (B)). The molar ratio of the carboxyl group of component (A) to component (B) is 79:21 to 40:60, and the above-mentioned component (B) satisfies at least one of the following conditions (1) and (2).

[0033] (1) The above polyol has a viscosity of less than 900 mPa·s at 20℃.

[0034] (2) The above polyols include at least one compound selected from the group consisting of hydrocarbon compounds substituted with 2 to 10 hydroxyl groups and polyalkylene glycols.

[0035] Such an adhesive can improve the permeability of the filler material and obtain a cured body with excellent strength.

[0036] <Component A: Carboxyl-containing polymer>

[0037] The carboxyl-containing polymer contained in the adhesive of this embodiment has a weight-average molecular weight (Mw) of 2000 g / mol to 6000 g / mol. By including such a carboxyl-containing polymer, an adhesive with excellent impregnation properties can be obtained. The weight-average molecular weight of the carboxyl-containing polymer is preferably 2500 g / mol to 6000 g / mol, more preferably 3000 g / mol to 6000 g / mol.

[0038] Furthermore, the number-average molecular weight (Mn) of the carboxyl-containing polymer is preferably 1000 g / mol to 4000 g / mol, more preferably 1500 g / mol to 3000 g / mol. The polydispersity (Mw / Mn) of the carboxyl-containing polymer is preferably 1 to 3, more preferably 1.4 to 2.5.

[0039] The weight-average molecular weight and number-average molecular weight of carboxyl-containing polymers can be determined by gel permeation chromatography (GPC) under the conditions described in the examples, for example.

[0040] The carboxyl-containing polymer of this embodiment preferably comprises structural units derived from monomers having olefinic unsaturated groups and carboxyl groups (hereinafter also referred to as unsaturated carboxylic acid monomers). There are no particular limitations on the unsaturated carboxylic acid monomer; for example, compounds represented by the following general formula (I) can be listed. It should be noted that, in this specification, the carboxyl group includes both carboxylic acid groups (-COOH) and salts of carboxylic acid groups.

[0041]

[0042] In general formula (1), R 1 R 2 and R 3 Same or different indicates hydrogen atom, methyl group, or -(CH2). z COOM 1 base, -(CH2) z COOM 1 The group can be combined with -COOX groups or other -(CH2) groups. z COOM 1 The radical forms anhydride, z is an integer from 0 to 2, M 1 [The symbol represents a hydrogen atom, alkali metal, alkaline earth metal, ammonium ion, organic ammonium ion, or organic amine group; X represents a hydrogen atom, methyl, ethyl, alkali metal, alkaline earth metal, ammonium ion, organic ammonium ion, or organic amine group.]

[0043] Examples of unsaturated carboxylic acid monomers represented by general formula (1) include: monocarboxylic acid monomers such as (meth)acrylic acid and crotonic acid, or their salts; dicarboxylic acid monomers such as maleic acid, itaconic acid, and fumaric acid, or their salts; anhydrides of dicarboxylic acid monomers such as maleic acid, itaconic acid, and fumaric acid, or their salts; etc. Examples of salts mentioned herein include: alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, organic amine salts, etc. Examples of alkali metal salts include: lithium salts, sodium salts, potassium salts, etc. Examples of alkaline earth metal salts include: calcium salts, magnesium salts, etc. Examples of organic ammonium salts include: methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethyl ammonium salts, triethyl ammonium salts, etc. Examples of organic amine salts include: ethanolamine salts, diethanolamine salts, triethanolamine salts, and other alkanolamine salts, etc.

[0044] From the viewpoint of further demonstrating the effects of this disclosure, as an unsaturated carboxylic acid monomer represented by general formula (1), (meth)acrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride are preferred, acrylic acid or a salt thereof, maleic acid or a salt thereof are more preferred, and acrylic acid is even more preferred.

[0045] Unsaturated carboxylic acid monomers can be used in single or multiple ways.

[0046] In adhesives, the carboxyl groups in carboxyl-containing polymers may or may not be neutralized. Of the carboxyl groups in carboxyl-containing polymers, 80 mol% or more may be carboxylic acid groups (i.e., unneutralized COOH groups), 90 mol% or more may be carboxylic acid groups, and 95 mol% or more may be carboxylic acid groups.

[0047] Neutralization of carboxyl-containing polymers can be achieved by adding a neutralizing agent during or after the synthesis of the carboxyl-containing polymer, preferably after synthesis. When the (C) component described later is added to the binder, it is preferable to add the neutralizing agent, (B) polyol, and (C) polyamine sequentially to the synthesized carboxyl-containing polymer.

[0048] Carboxyl-containing polymers may contain structural units derived from monomers other than unsaturated carboxylic acid monomers (hereinafter also referred to as other monomers). Examples of other monomers include monomers having olefinic unsaturated groups and hydroxyl groups (hereinafter also referred to as unsaturated alcohols); alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and lauryl methacrylate; amino-containing acrylates such as dimethylaminoethyl methacrylate or its salts; amide-containing monomers such as methacrylamide, dimethacrylamide, and isopropylacrylamide; vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide and phenylmaleimide. Maleimide derivatives such as imides and cyclohexylmaleimides; vinyl monomers containing nitrile groups such as (meth)acrylonitrile; monomers or their salts containing sulfonic acid groups such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrene sulfonic acid, and vinyl sulfonic acid; monomers containing phosphonic acid groups such as vinylphosphonic acid, allylphosphonic acid, and methylallylphosphonic acid; vinyl monomers containing aldehyde groups such as (meth)acrylonitrile; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; and monomers containing other functional groups such as vinyl chloride, vinylidene chloride, allyl alcohol, and vinylpyrrolidone. They can be used individually or in combination with two or more groups.

[0049] Examples of unsaturated alcohols that have olefinic unsaturated groups and hydroxyl groups include: allyl alcohol, β-methyl allyl alcohol, isoprene alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, and compounds represented by the following general formula (2).

[0050]

[0051] In the above general formula (2), R 4 R represents a hydrogen atom or a methyl group. 5 This refers to organic groups with 2 to 20 carbon atoms.

[0052] R in the above general formula (2) 5Specific examples include: alkylene groups such as -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, -C(CH3)2-, -CH2CH2CH2-, -CH(C2H5)CH2-, -C(C2H5)(CH3)-, -CH2CH2CH2CH2-, and -CH(C4H9)CH2-; arylene groups such as phenylene and naphthyl; ether groups such as -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2OCH2CH2-, -CH(CH3)CH2OCH(CH3)CH2-, and -CH(CH3)CH2OCH(CH3)CH2OCH(CH3)CH2-; etc.

[0053] Relative to 100 mol% of all structural units contained in the carboxyl-containing polymer, the content of structural units derived from unsaturated alcohols in the carboxyl-containing polymer is preferably 15 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less. The carboxyl-containing polymer may not contain structural units derived from unsaturated alcohols.

[0054] Relative to 100 mol% of all structural units contained in the carboxyl-containing polymer, the content of structural units derived from unsaturated carboxylic acid monomers in the carboxyl-containing polymer is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. The carboxyl-containing polymer may not contain any structural units other than those derived from unsaturated carboxylic acid monomers.

[0055] The carboxyl-containing polymer in this embodiment can be a homopolymer containing only structural units derived from one monomer, or it can be a copolymer containing structural units derived from two or more monomers. When the carboxyl-containing polymer is a copolymer, it can be a random copolymer or a block copolymer.

[0056] It should be noted that structural units derived from unsaturated carboxylic acid monomers and structural units derived from other monomers are formed through the free radical polymerization of unsaturated carboxylic acid monomers and other monomers, respectively. However, in reality, even structural units not formed through the free radical polymerization of monomers can be formed through other methods as long as they have the same chemical structure as structural units formed through free radical polymerization.

[0057] The carboxyl-containing polymer of this embodiment may contain phosphorus. The phosphorus may be derived from phosphorus-containing compounds used, for example, as chain transfer agents during the synthesis of the carboxyl-containing polymer. That is, in this case, the phosphorus is contained in the residues of the phosphorus-containing compound bound to the carboxyl-containing polymer. When the carboxyl-containing polymer contains phosphorus, the curing reaction of the binder can be promoted, which is therefore preferable.

[0058] Examples of phosphorus-containing compounds include: hypophosphorous acid (salt), phosphorous acid (salt), phosphate (salt), pyrophosphate (salt), polyphosphate (salt), organophosphate (salt), and other phosphorus-containing oxyacids or salts. The phosphorus content in the carboxyl-containing polymer, calculated as a phosphorus-containing compound relative to 100% by mass, is preferably 0% to 20% by mass, more preferably 0.1% to 15% by mass, and even more preferably 0.5% to 10% by mass. One or more phosphorus-containing compounds may be present as residues in the carboxyl-containing polymer.

[0059] Relative to 100% by mass of the total amount of adhesive, the content of component (A) in the adhesive of this embodiment is preferably 10% to 90% by mass, more preferably 20% to 80% by mass.

[0060] The polymer of this embodiment can be obtained by polymerizing the aforementioned unsaturated carboxylic acid monomers and other monomers using conventionally known methods. For example, a polymer manufactured by solution polymerization is preferred, in which the aforementioned unsaturated carboxylic acid monomers and other monomers are polymerized in water, in the presence of a polymerization initiator and a chain transfer agent, under reflux conditions. Sodium persulfate is preferred as the polymerization initiator. Sodium bisulfate is preferred as the chain transfer agent.

[0061] <(B) Ingredient: Polyols>

[0062] The polyol of this embodiment satisfies at least one of the following conditions (1) and (2). The polyol may satisfy both conditions (1) and (2).

[0063] (1) It has a viscosity of less than 900 mPa·s at 20℃.

[0064] (2) Contains at least one compound selected from the group consisting of hydrocarbon compounds substituted with 2 to 10 hydroxyl groups (hereinafter also referred to as component (B1)) and polyalkylene glycols (hereinafter also referred to as component (B2)). The polyol mainly functions as a crosslinking agent for crosslinking carboxyl-containing polymers in the curing reaction of the adhesive.

[0065] When such polyols are used in adhesives, the viscosity of the adhesive can be prevented from increasing, thus improving its permeability. Furthermore, unlike previously used polyols containing amino groups such as diethanolamine and triethanolamine, the protonation of the amino groups increases the pH in the adhesive, reducing concerns about a decrease in the strength of the cured body due to hindered curing reactions.

[0066] The viscosity of the polyol at 20°C is preferably 500 mPa·s or less, more preferably 250 mPa·s or less, even more preferably 100 mPa·s or less, and particularly preferably 50 mPa·s or less. It should be noted that the viscosity of the polyol refers to the viscosity of each polyol as a pure substance (i.e., as a liquid in a single-component system). Examples of polyols with such viscosity include: ethylene glycol (20 mPa·s), diethylene glycol (36 mPa·s), 1,2-propanediol (56 mPa·s), 1,4-butanediol (98 mPa·s), tetraethylene glycol (55 mPa·s), 1,2-pentanediol (180 mPa·s (20°C)), 2-methyl-2,4-pentanediol (34 mPa·s), and 3-methyl-1,5-pentanediol (173 mPa·s), etc. (The values ​​in parentheses are the viscosities of each compound at 20°C). It should be noted that viscosity can be measured, for example, using a type B viscometer.

[0067] (B1) The component is a compound obtained by replacing 2 to 10 hydrogen atoms of a hydrocarbon compound with a hydroxyl group. It should be noted that, in this specification, "obtained by substitution" is a term that formally represents the chemical structure, and actually refers not only to compounds obtained by replacing hydrogen atoms with hydroxyl groups. Therefore, any compound having a chemical structure obtained by replacing 2 to 10 hydrogen atoms of a hydrocarbon compound with a hydroxyl group can be a compound obtained through a chemical reaction other than the direct substitution of hydrogen atoms with hydroxyl groups, and can also be a natural product.

[0068] Component (B1) may have 2 to 8 hydroxyl groups, 2 to 5 hydroxyl groups, or 2 or 3 hydroxyl groups. Component (B1) may have 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 5 carbon atoms. The aforementioned hydrocarbon compound may be an aliphatic hydrocarbon compound or an aromatic hydrocarbon compound. The aliphatic hydrocarbon compound may be a saturated hydrocarbon compound or an unsaturated hydrocarbon compound, preferably a saturated hydrocarbon compound. The aliphatic hydrocarbon compound may be a chain-like aliphatic hydrocarbon compound or an aliphatic hydrocarbon compound containing a cyclic structure.

[0069] As components (B1), examples include: ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and other alkane diols; glycerol, trimethylolpropane, trimethylolethane, erythritol, xylitol, sorbitol, and other ternary or higher alcohols.

[0070] As a component of (B2), for example, compounds represented by the following general formula (3) can be listed.

[0071]

[0072] (In general formula (3), A) 1 It is a divalent hydrocarbon group with 2 to 5 carbon atoms, n is 2 to 20, and within one molecule, A 1 It can be just one type, or it can be two or more types.

[0073] In general formula (3), divalent hydrocarbon groups can be listed as ethylene, 1,3-propylene, 1,2-propyl, 1,4-butylene, 1,3-butylene, etc., and may contain one or more of them. n can be the average number of molecules based on the total number of molecules of component (B2) (i.e., a rational number), or it can be an integer. n is preferably 2 to 10, and can be 2 to 5.

[0074] As a component (B2), examples include diethylene glycol, triethylene glycol, tetraethylene glycol, and other polyalkylene glycols.

[0075] From the viewpoint of further improving the impregnation of the adhesive, the molecular weight of the polyol is preferably 1000 g / mol or less, more preferably 500 g / mol or less, and even more preferably 200 g / mol or less.

[0076] From the viewpoint of improving the permeability of the adhesive and the mechanical strength of the resulting cured body, the molar ratio of the carboxylic acid group of component (A) to component (B) in the adhesive (molar amount of carboxylic acid group of component (A): molar amount of component (B)) is 79:21 to 35:65, preferably 75:25 to 40:60, and more preferably 70:30 to 40:60.

[0077] Relative to 100% by mass of the total amount of adhesive, the content of component (B) in the adhesive of this embodiment is preferably 5% to 60% by mass, more preferably 7% to 50% by mass.

[0078] <Other Ingredients>

[0079] The adhesive of this embodiment may contain components other than components (A) and (B). For example, the adhesive may also contain at least one of a polyamine (hereinafter also referred to as component (C)) and a silane coupling agent (hereinafter also referred to as component (D)).

[0080] As for the (C) polyamine, there is no particular problem as long as it is a compound having two or more amino groups in the molecule, but amine compounds with four or more nitrogen atoms per molecule are preferred. Examples of (C) polyamines include polyalkylene polyamines, polyamide polyamines, polyalkylene imide epoxides, and polyethyleneamines, with polyalkylene polyamines being preferred. Examples of polyalkylene polyamines include polymers or copolymers of one or more alkylene imides as monomers (i.e., polyalkylene imides), alkylene imide adducts of aliphatic polyamines, etc. Polyalkylene imides are preferably polymers or copolymers of alkylene imides having 2 to 8 carbon atoms (more preferably 2 to 6), more preferably polymers or copolymers of one or more alkylene imides selected from the group consisting of ethylene imide, propylene imide, 1,2-butylene imide, 2,3-butylene imide, and 1,1-dimethylethylene imide, and even more preferably polymers of ethylene imide (polyethyleneimide). As an alkylene imine adduct of an aliphatic polyamine, it is preferably a (ring-opening addition) adduct obtained by adding an alkylene imine to 2 to 6 alkylene diamines (e.g., ethylenediamine). The alkylene imine used as the adduct is preferably an alkylene imine monomer exemplified as a polyalkylene imine. It should be noted that the aforementioned polyalkylene imine and adduct do not necessarily have to be substances produced by directly polymerizing or subjecting the alkylene imine to an addition reaction; they can also be substances synthesized through other chemical reactions, as long as they have the same chemical structure as the aforementioned polyalkylene imine and adduct. The number-average molecular weight of polyamines can range from 200 g / mol to 500,000 g / mol, from 250 g / mol to 100,000 g / mol, from 250 g / mol to 80,000 g / mol, from 300 g / mol to 50,000 g / mol, from 400 g / mol to 10,000 g / mol, or from 500 g / mol to 5,000 g / mol. Only one type of polyamine can be used, or two or more can be used in combination. It should be noted that (C) polyamines preferably do not contain hydroxyl groups.

[0081] The content of component (C) in the adhesive is preferably 0.01 to 5 parts by mass relative to the total mass of components (A) and (B) of 100 parts by mass, and more preferably 0.1 to 3 parts by mass.

[0082] When the binder contains component (D), component (D) acts at the interface between the filler and the binder, tending to improve the penetration of the binder and the strength of the resulting cured body. Examples of silane coupling agents include: aminosilane coupling agents such as γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane; and epoxysilane coupling agents such as γ-epoxypropoxypropyltrimethoxysilane and γ-epoxypropoxypropylmethyldimethoxysilane. One or more of these can be used in combination.

[0083] The content of silane coupling agent in the binder is preferably 0.01 to 5 parts by mass relative to the total mass of components (A) and (B) of 100 parts by mass, and more preferably 0.1 to 3 parts by mass.

[0084] The binder may also contain free phosphorus-containing compounds. Phosphorus compounds are considered to have a promoting effect on the cross-linking of component (A), and are therefore preferred. Examples of free phosphorus-containing compounds include: phosphoric acid (salt), phosphorous acid (salt), phosphate (salt), pyrophosphate (salt), polyphosphate (salt), organophosphate (salt), and other phosphorus-containing oxyacids or their salts or esters (including their hydrates); organophosphorus compounds such as trimethylphosphine, triphenylphosphine, and triphenylphosphine oxide; etc. When the binder contains phosphorus-containing compounds, it may contain one or more of these compounds. Examples of salts include the salts described above. The content of the above-mentioned phosphorus-containing compounds in the binder relative to 100% by mass of component (A) is preferably set to 20% by mass or less, more preferably 0.1% by mass to 10% by mass, and even more preferably 0.5% by mass to 7% by mass. It should be noted that when component (A) contains phosphorus, the content of phosphorus-containing compounds can be the sum of the content of phosphorus in component (A) (converted to free phosphorus-containing compounds) and the content of free phosphorus-containing compounds.

[0085] The binder may also contain curing accelerators other than phosphorus compounds. Examples of such curing accelerators include: protic acids (sulfuric acid, carboxylic acid, carbonic acid, etc.) and their salts (metal salts (alkali metals, alkaline earth metals, transition metals, Group 2B, Group 4A, Group 4B, Group 5B, etc.), ammonium salts, etc.), oxides, chlorides, hydroxides, alkoxides, etc. of the aforementioned metals. Only one of these substances may be used, or two or more may be used.

[0086] The adhesive may contain a solvent. The solvent may be an organic solvent, but water is preferred. That is, the adhesive may be an aqueous solution. The water content in the adhesive (aqueous solution) is preferably 10% to 80% by mass relative to 100% of the total amount of the adhesive, more preferably 20% to 70% by mass, and even more preferably 25% to 60% by mass.

[0087] Furthermore, the adhesive can be in anhydrous form or contain only a small amount of water. In this case, the water content in the adhesive can be less than 10% by mass relative to 100% of the total adhesive volume, which can be less than 5% by mass or less than 1% by mass. Such an adhesive can be used directly or diluted with solvents such as water before use, depending on the intended application.

[0088] Adhesives may also contain additives such as rust inhibitors, colorants, dust suppressants such as heavy oil-water dispersions, and inorganic sulfates (neutralizing agents). Inorganic sulfates have the function of neutralizing alkaline components dissolved from inorganic fibers such as glass; ammonium sulfate is an example. Relative to 100% by mass of the total amount of the adhesive after solvent removal, the content of components (A) and (B) in the adhesive can be 90% by mass or more, or 95% by mass or more.

[0089] From the viewpoint of further improving permeability, the viscosity of the binder at 25°C is preferably 200 mPa·s or less, more preferably 180 mPa·s or less, even more preferably 160 mPa·s or less, even more preferably 120 mPa·s or less, and particularly preferably 100 mPa·s or less. The viscosity of the binder can be appropriately adjusted by adjusting the mixing ratio of component (A) and component (B) and the water content. It should be noted that the viscosity can be measured, for example, using a type B viscometer.

[0090] The pH of the adhesive is preferably 1 to 4.0, more preferably 1.5 to 3.7 or less, and even more preferably 2 to 3.5.

[0091] <Filling Material>

[0092] The adhesive of this embodiment can be appropriately used for bonding filler materials (bonded materials). There are no particular limitations on the filler material; it can be either inorganic or organic. Furthermore, there are no particular limitations on the shape of the filler material; it can be any shape, such as fibrous or granular. As a fibrous filler material, it can be either woven or nonwoven fabric. Because of its excellent impregnation properties, the adhesive of this embodiment is useful as a fiber adhesive, and is particularly useful when used in the case of nonwoven fabrics.

[0093] Examples of inorganic fillers include: inorganic fibers such as glass fiber, asbestos, and carbon fiber (which can be either woven or nonwoven fabric, preferably nonwoven fabric); inorganic particles such as powdered glass, glass beads, and mineral particles (inorganic powders). Among these materials, glass fiber or powdered glass is preferred from the perspective that the cured body can be widely used as a thermal insulation material. The binder of this embodiment is particularly useful when bonding glass nonwoven fabric fibers (e.g., glass wool).

[0094] Examples of organic fillers include: fibers of organic materials such as wool, cellulose, hemp, nylon, and polyester; and particles of organic materials such as nylon microparticles and polyester microparticles (powders of organic materials).

[0095] <Solid body>

[0096] The cured body of this embodiment comprises a cured product of the aforementioned adhesive and a filler material bonded by the cured product. That is, the cured body of this embodiment may also be a composite material comprising a cured product of an adhesive and a filler material.

[0097] <Method for manufacturing cured body>

[0098] There are no particular limitations on the method for manufacturing the cured body, as long as it includes a step of curing the precursor obtained by contacting the aforementioned components (A) and (B) with a filler material. Components (A) and (B) can be mixed in advance with other components at a predetermined molar ratio to prepare an adhesive, and the precursor can be produced by contacting the adhesive with the filler material (e.g., impregnating the filler material with the adhesive or mixing the adhesive with the filler material). Alternatively, the step of preparing the adhesive in advance may not be included. In the absence of the adhesive preparation step, for example, the precursor can be produced by adding components (A) and (B) and other components as needed to the filler material one at a time or sequentially and mixing or impregnating them. The precursor can be shaped into a desired form before the curing step described later.

[0099] Relative to 100 parts by weight of filler material, the binder content in the precursor, calculated in terms of solid content, is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and even more preferably 1 to 15 parts by weight. When the amount of binder adhering is within the above range, the mechanical strength of the manufactured cured body tends to be improved.

[0100] After the precursor is prepared, the precursor is cured by curing the binder contained in the precursor. One method for curing the precursor is by heating it (heating process). The heating temperature and heating time in the heating process can be set, for example, 100°C to 300°C and 1 minute to 120 minutes. From an operability point of view, a low temperature and short time are preferred. For example, the heating temperature is preferably 120°C to 250°C, more preferably 140°C to 230°C, and even more preferably 150°C to 200°C. Furthermore, the heating time is preferably 1 minute to 60 minutes, more preferably 1 minute to 45 minutes, and even more preferably 1 minute to 30 minutes.

[0101] Furthermore, the adhesive of this embodiment tends to have low-temperature curing and rapid curing properties, which is advantageous from the viewpoint of saving energy during the curing reaction and shortening the curing time. For example, the complete curing temperature can be used as an indicator of the low-temperature curing and rapid curing properties of the adhesive. The complete curing temperature of the adhesive is preferably 195°C or below, more preferably 185°C or below, even more preferably 180°C or below, even more preferably 175°C or below, and particularly preferably 165°C or below.

[0102] The complete curing temperature of the adhesive can be determined using a dynamic viscoelasticity measuring device at a heating rate of 4°C / min from 30°C to 250°C. The temperature at which the storage modulus becomes constant is taken as the complete curing temperature of the adhesive.

[0103] [Example]

[0104] The following examples illustrate the present disclosure in more detail, but the present disclosure is not limited to these examples. It should be noted that, unless otherwise specified, "%" means "mass %".

[0105] As component (A), carboxyl-containing polymers having various weight-average molecular weights are prepared as described below. The weight-average molecular weight and solid content of component (A) are determined under the following conditions.

[0106] <Determination conditions of weight-average molecular weight (Mw)>

[0107] The weight-average molecular weight (Mw) was determined under the following conditions.

[0108] Device: HLC-8320GPC manufactured by Tosoh Corporation

[0109] Detector: RI

[0110] Pillar: Manufactured by Tosoh Corporation, TSK-GEL G3000PWXL

[0111] Column temperature: 35℃

[0112] Flow rate: 0.5 mL / min

[0113] Calibration curve: Sodium polyacrylate standard manufactured by Chuanghe Science Co., Ltd.

[0114] Eluent: A solution obtained by diluting a mixture of sodium dihydrogen phosphate dodecahydrate / disodium hydrogen phosphate dihydrate (34.5g / 46.2g) with pure water to 5000g.

[0115] <Method for determining the solid content of polymer aqueous solution after polymerization>

[0116] The polymer aqueous solution was dried in an oven heated to 130°C for 60 minutes. The solid content (%) of the polymer aqueous solution after polymerization was calculated from the weight change before and after drying.

[0117] <Manufacturing Example 1>

[0118] 316.3 g of pure water (initial charge) was added to a 2.5-liter detachable stainless steel flask equipped with a reflux cooler, a stirrer (paddle blades), and a thermometer, and heated to the boiling point with stirring. Then, with stirring, the materials were added dropwise through their respective feed paths to the polymerization reaction system in its boiling reflux state at the following feed rates: 900.0 g (10.0 mol) of 80% acrylic acid aqueous solution (hereinafter referred to as "80% AA") for 180 minutes; 71.0 g of 15% sodium persulfate aqueous solution (hereinafter referred to as "15% NaPS") for 195 minutes; and 25.7 g of 45% sodium hypophosphite aqueous solution (hereinafter referred to as "45% SHP") in two stages for 18 minutes, followed by 101.7 g for 162 minutes. The addition of each component, except for 45% SHP, was carried out continuously at a constant dropping rate. After the addition of 80% AA, the reaction solution was further maintained under boiling reflux for 30 minutes (aging) to complete the polymerization. After polymerization, 417.8 g of pure water was added to the reaction solution to obtain an aqueous solution with a solid content of 44.3%, a number-average molecular weight of 1920, and a weight-average molecular weight of 3080 (polydispersity: 1.60). Hereinafter, the obtained polymer will also be referred to as PAA3000.

[0119] <Manufacturing Example 2>

[0120] 329.0 g of pure water (initial charge) was added to a 2.5-liter detachable stainless steel flask equipped with a reflux cooler, a stirrer (paddle blades), and a thermometer. The mixture was heated to its boiling point with stirring. Then, with stirring, the materials were added dropwise through their respective feed paths to the polymerization reaction system in its boiling reflux state at the following rates: 900.0 g (10.0 mol) of 80% acrylic acid aqueous solution (hereinafter referred to as "80% AA") for 180 minutes; 59.2 g of 15% sodium persulfate aqueous solution (hereinafter referred to as "15% NaPS") for 195 minutes; and 21.4 g of 45% sodium hypophosphite aqueous solution (hereinafter referred to as "45% SHP") in two stages for 18 minutes, followed by 84.8 g for 162 minutes. The addition of each component, except for 45% SHP, was carried out continuously at a constant dropping rate. After the addition of 80% AA, the reaction solution was further maintained under boiling reflux for 30 minutes (aging) to complete the polymerization. After polymerization, 411.8 g of pure water was added to the reaction solution to obtain an aqueous solution with a solid content of 44.7%, a number-average molecular weight of 2260, and a weight-average molecular weight of 4080 (polydispersity: 1.81). Hereinafter, the obtained polymer will also be referred to as PAA4000.

[0121] <Manufacturing Example 3>

[0122] 437.4 g of pure water (initial charge) was added to a 2.5-liter detachable stainless steel flask equipped with a reflux cooler, a stirrer (paddle blades), and a thermometer. The mixture was heated to its boiling point with stirring. Then, with stirring, the materials were added dropwise through their respective feed paths to the polymerization reaction system in its boiling reflux state at the following rates: 1560.0 g (17.3 mol) of 80% acrylic acid aqueous solution (hereinafter referred to as "80% AA") over 180 minutes; 55.0 g of 15% sodium persulfate aqueous solution (hereinafter referred to as "15% NaPS") over 195 minutes; and 26.9 g of 45% sodium hypophosphite aqueous solution (hereinafter referred to as "45% SHP") over two stages, followed by 107.7 g over 162 minutes. The addition of each component, except for 45% SHP, was carried out continuously at a constant dropping rate. After the addition of 80% AA, the reaction solution was further maintained under boiling reflux for 30 minutes (aging) to complete the polymerization. After polymerization, 207.2 g of pure water was added to the reaction solution to obtain an aqueous solution with a solid content of 56.3%, a number-average molecular weight of 2890, and a weight-average molecular weight of 5980 (polydispersity: 2.07). Hereinafter, the obtained polymer will also be referred to as PAA6000.

[0123] <Manufacturing Example 4>

[0124] 401.8 g of pure water (initial charge) was added to a 2.5-liter detachable stainless steel flask equipped with a reflux cooler, a stirrer (paddle blades), and a thermometer. The mixture was heated to its boiling point with stirring. Then, with stirring, the materials were added dropwise through their respective feed paths to the polymerization reaction system in its boiling reflux state at the following rates: 1200.0 g (13.3 mol) of 80% acrylic acid aqueous solution (hereinafter referred to as "80% AA") for 180 minutes; 42.3 g of 15% sodium persulfate aqueous solution (hereinafter referred to as "15% NaPS") for 195 minutes; and 15.9 g of 45% sodium hypophosphite aqueous solution (hereinafter referred to as "45% SHP") in two stages, for 18 minutes, followed by 63.8 g for 162 minutes. The addition of each component, except for 45% SHP, was carried out continuously at a constant dropping rate. After the addition of 80% AA, the reaction solution was further maintained under boiling reflux for 30 minutes (aging) to complete the polymerization. After polymerization, 269.9 g of the reaction solution was added to obtain an aqueous solution (PAA8000). This aqueous solution (PAA8000) had a solids content of 51.5%, a number-average molecular weight of 3570, and a weight-average molecular weight of 8070 (polydispersity: 2.26). Hereinafter, the obtained polymer will also be referred to as PAA8000.

[0125] <Manufacturing Example 5>

[0126] 400.0 g of pure water (initial charge) was added to a 2.5 L stainless steel detachable flask equipped with a reflux cooler, a stirrer (paddle blades), and a thermometer. The mixture was heated to its boiling point with stirring. Then, with stirring, the materials were added dropwise through their respective feed paths to the polymerization reaction system in its boiling reflux state at the following feed rates: 1051.8 g (11.7 mol) of 80% acrylic acid aqueous solution (hereinafter referred to as "80% AA") over 180 minutes; 35.4 g of 15% sodium persulfate aqueous solution (hereinafter referred to as "15% NaPS") over 195 minutes; and 5.5 g of 45% sodium hypophosphite aqueous solution (hereinafter referred to as "45% SHP") over two stages, followed by 22.0 g over 162 minutes. The addition of each component, except for 45% SHP, was carried out continuously at a constant dropping rate. After the addition of 80% AA, the reaction solution was further maintained under boiling reflux for 30 minutes (aging) to complete the polymerization. After polymerization, 165.8 g of pure water was added to the reaction solution to obtain an aqueous solution with a solid content of 52.4%, a number-average molecular weight of 7410, and a weight-average molecular weight of 29290 (polydispersity: 3.95). Hereinafter, the obtained polymer will also be referred to as PAA30000.

[0127] The adhesives of Examples 1-20 and Comparative Examples 1-11 were prepared by combining (A) a carboxyl-containing polymer, (B) a polyol, (C) a polyamine, and (D) a silane coupling agent in the proportions shown in Tables 1-3. For each adhesive obtained, appropriate amounts of water were added and various performance evaluations were performed as shown below. The results are shown in Tables 1-3.

[0128] The viscosity of the polyol as component (B) at 20°C is as follows.

[0129] Ethylene glycol: 20 mPa·s

[0130] Diethylene glycol: 36 mPa·s

[0131] Tetraethylene glycol: 55 mPa·s

[0132] 1,4-Butanediol: 98 mPa·s

[0133] Diethanolamine: 1000 mPa·s

[0134] Triethanolamine: 1013 mPa·s

[0135] It should be noted that in Tables 1-3, the content of component (A) is the amount (moles) of structural units derived from acrylic acid, and the content of component (B) is in moles.

[0136] In addition, the abbreviations or abbreviations of the components in Tables 1 to 3 are as follows.

[0137] <(C) Ingredient: Polyamine>

[0138] PEI(1): Polyethyleneimine (trade name: Epomin (registered trademark) SP-006, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 600 (determined by boiling point elevation method))

[0139] PEI(2): Polyethyleneimine (trade name: Epomin (registered trademark) P-1000, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 70,000 (determined by viscosity method))

[0140] <(D) Ingredient: Silane Coupling Agent>

[0141] Silane I: γ-Epoxypropoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0142] Aminosilane: γ-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0143] It should be noted that in Tables 1-3, the contents of component (C) and component (D) are parts by mass relative to the total contents of component (A) and component (B) of 100 parts by mass.

[0144] <Production of Experimental Films>

[0145] Test pieces for mechanical strength testing are prepared in the following manner.

[0146] (i) Pure water was added to the adhesive to dilute it to 35% by mass, thus preparing an aqueous adhesive solution.

[0147] (ii) Add the binder aqueous solution obtained in (i) to glass beads with a particle size of 0.50 mm to 0.150 mm, such that the binder aqueous solution is 5.0% of the mass of the glass beads, and mix thoroughly to obtain a mixture.

[0148] (iii) The mixture obtained in (ii) was pressed into a 120mm×20mm×5mm mold box that had been demolded and shaped. It was dried in an oven at 210°C for 30 minutes and then cooled at room temperature for 30 minutes to obtain the test piece.

[0149] <Mechanical strength of the test piece>

[0150] For the above test pieces, the bending strength was determined according to JIS K 7171 at a test speed of 2 mm / min. The bending strength of 3 test pieces was measured, and the average value was calculated.

[0151] <Evaluation Methods for the Impregnation of Glass Beads>

[0152] 30g of glass beads with a particle size of 0.50mm to 0.150mm were spread evenly in a 120mm diameter petri dish. 3g of the aforementioned binder aqueous solution was slowly added dropwise towards the center of the dish. After the addition was complete, the area of ​​the binder spread on the glass beads was calculated after 10 seconds. The area was classified according to the following criteria to evaluate the permeability.

[0153] A: 25cm 2 above

[0154] B: 20cm 2 Above and below 25cm 2

[0155] C: Less than 20cm 2

[0156] <Evaluation Method for Complete Curing Temperature>

[0157] The temperature was measured from 30°C to 250°C using a dynamic viscoelasticity measuring device (DMA) at a heating rate of 4°C / min, and the temperature at which the storage modulus was kept constant was taken as the complete curing temperature.

[0158] <Methods for pH Measurement>

[0159] At 25°C, the pH value of the adhesive aqueous solution, obtained by diluting the adhesive to 50% with pure water, was measured using a pH meter (manufactured by HORIBA, trade name "D-51"). The results are shown in Tables 1-3.

[0160] <Methods for measuring viscosity>

[0161] At 25°C, the viscosity of an aqueous adhesive solution diluted to 50% with pure water was measured using a Type B viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a rotation speed of 30 rpm. An appropriate rotor was used based on the viscosity range measured. The results are shown in Tables 1-3.

[0162]

[0163]

[0164]

Claims

1. An adhesive comprising: Carboxyl-containing polymers and polyols with a weight-average molecular weight of 2000 g / mol to 6000 g / mol. The carboxyl-containing polymer comprises homopolymers containing only structural units derived from acrylic acid. The molar ratio of the carboxylic acid group in the carboxyl-containing polymer to the polyol is 60:40 to 35:

65. The polyol is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, erythritol, xylitol, and sorbitol.

2. The adhesive as claimed in claim 1, wherein, The polyol comprises a polyol having a viscosity of less than 900 mPa·s at 20°C.

3. The adhesive as described in claim 1 or 2, wherein, The weight-average molecular weight of the carboxyl-containing polymer is 2500 g / mol to 6000 g / mol.

4. The adhesive as claimed in claim 1 or 2, wherein, The weight-average molecular weight of the carboxyl-containing polymer is 3000 g / mol to 6000 g / mol.

5. The adhesive as described in claim 1 or 2, wherein, The number-average molecular weight (Mn) of the carboxyl-containing polymer is 1000 g / mol to 4000 g / mol.

6. The adhesive as claimed in claim 1 or 2, wherein, The number-average molecular weight (Mn) of the carboxyl-containing polymer is 1500 g / mol to 3000 g / mol.

7. The adhesive as claimed in claim 1 or 2, wherein, The polydispersity (Mw / Mn) of the carboxyl-containing polymer is 1 to 3.

8. The adhesive as claimed in claim 1 or 2, wherein, The polydispersity (Mw / Mn) of the carboxyl-containing polymer is 1.4 to 2.

5.

9. The adhesive as claimed in claim 1 or 2, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 80 mol% are COOH groups.

10. The adhesive as claimed in claim 1 or 2, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 90 mol% are COOH groups.

11. The adhesive as claimed in claim 1 or 2, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 95 mol% are COOH groups.

12. The adhesive as claimed in claim 1 or 2, wherein, The carboxyl-containing polymer contains phosphorus.

13. The adhesive as claimed in claim 1 or 2, wherein, The carboxyl-containing polymer contains residues derived from phosphorus-containing oxyacids.

14. The adhesive as claimed in claim 1 or 2, wherein, The carboxyl-containing polymer contains residues of hypophosphoric acid or its salts, phosphorous acid or its salts, phosphoric acid or its salts, pyrophosphoric acid or its salts, polyphosphoric acid or its salts, or organic phosphoric acid or its salts.

15. The adhesive as claimed in claim 1 or 2, wherein, The content of the carboxyl-containing polymer is 10% to 90% by mass relative to 100% of the total amount of the binder.

16. The adhesive as claimed in claim 1 or 2, wherein, The content of the carboxyl-containing polymer is 20% to 80% by mass relative to 100% of the total amount of the binder.

17. The adhesive as claimed in claim 1 or 2, wherein, The polyol has a viscosity of less than 500 mPa·s at 20°C.

18. The adhesive as claimed in claim 1 or 2, wherein, The polyol has a viscosity of less than 250 mPa·s at 20°C.

19. The adhesive as claimed in claim 1 or 2, wherein, The polyol has a viscosity of less than 100 mPa·s at 20°C.

20. The adhesive as claimed in claim 1 or 2, wherein, The polyol has a viscosity of less than 50 mPa·s at 20°C.

21. The adhesive as claimed in claim 1 or 2, wherein, The polyol has 2 to 5 hydroxyl groups.

22. The adhesive as claimed in claim 1 or 2, wherein, The polyol has two or three hydroxyl groups.

23. The adhesive as claimed in claim 1 or 2, wherein, The polyol has 2 to 5 carbon atoms.

24. The adhesive as claimed in claim 1 or 2, wherein, The molar ratio of the carboxylic acid group in the carboxyl-containing polymer to the polyol is 60:40 to 40:

60.

25. The adhesive as claimed in claim 1 or 2, wherein, The content of the polyol in the adhesive is 5% to 60% by mass relative to 100% of the total amount of the adhesive.

26. The adhesive as claimed in claim 1 or 2, wherein, The content of the polyol in the adhesive is 7% to 50% by mass relative to 100% of the total amount of the adhesive.

27. The adhesive as claimed in claim 1 or 2, wherein, The adhesive also contains polyamines.

28. The adhesive of claim 27, wherein, The polyamine is an amine compound with 4 or more nitrogen atoms per molecule.

29. The adhesive of claim 27, wherein, The polyamine includes polyalkylene polyamine, polyamide polyamine, polyalkylene imine epoxy, or polyethyleneamine.

30. The adhesive of claim 27, wherein, The polyamine comprises polyalkylene polyamines.

31. The adhesive of claim 27, wherein, The polyamine comprises a polymer or copolymer with one or more alkylimines as monomers, or an alkylimine adduct of an aliphatic polyamine.

32. The adhesive of claim 27, wherein, The polyamine comprises a polymer or copolymer of an alkylimine having 2 to 8 carbon atoms.

33. The adhesive of claim 27, wherein, The polyamine comprises a polymer or copolymer of an alkylimine having 2 to 6 carbon atoms.

34. The adhesive of claim 27, wherein, The polyamine comprises a polymer or copolymer of one or more alkylene imides selected from the group consisting of ethylene imide, propylene imide, 1,2-butylene imide, 2,3-butylene imide and 1,1-dimethylethylene imide.

35. The adhesive of claim 27, wherein, The polyamine includes polyethyleneimine.

36. The adhesive of claim 27, wherein, The polyamine is an alkylimine adduct of an aliphatic polyamine obtained by ring-opening addition of alkylimines to 2 to 6 alkylimines.

37. The adhesive of claim 27, wherein, The polyamine is an alkylimine adduct of an aliphatic polyamine obtained by ring-opening addition of alkylimines to 2 to 6 ethylenediamines.

38. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 200 g / mol to 500,000 g / mol.

39. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 250 g / mol to 100,000 g / mol.

40. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 250 g / mol to 80,000 g / mol.

41. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 300 g / mol to 50,000 g / mol.

42. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 400 g / mol to 10000 g / mol.

43. The adhesive of claim 27, wherein, The number-average molecular weight of the polyamine is 500 g / mol to 5000 g / mol.

44. The adhesive of claim 27, wherein, The polyamine does not contain hydroxyl groups.

45. The adhesive of claim 27, wherein, The content of the polyamine in the binder is 0.01 to 5 parts by mass relative to 100 parts by mass of the combined amount of the carboxyl-containing polymer and the polyol.

46. ​​The adhesive of claim 27, wherein, The content of the polyamine in the binder is 0.1 to 3 parts by mass relative to 100 parts by mass of the combined amount of the carboxyl-containing polymer and the polyol.

47. The adhesive as claimed in claim 1 or 2, wherein, The adhesive also contains a silane coupling agent.

48. The adhesive of claim 47, wherein, The silane coupling agent comprises an aminosilane coupling agent or an epoxysilane coupling agent.

49. The adhesive of claim 47, wherein, The silane coupling agent comprises γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, or γ-epoxypropoxypropylmethyldimethoxysilane.

50. The adhesive of claim 47, wherein, The content of the silane coupling agent in the binder is 0.01 to 5 parts by mass relative to 100 parts by mass of the total mass of the carboxyl-containing polymer and the polyol.

51. The adhesive of claim 47, wherein, The content of the silane coupling agent in the binder is 0.1 to 3 parts by mass relative to 100 parts by mass of the total mass of the carboxyl-containing polymer and the polyol.

52. The adhesive as claimed in claim 1 or 2, wherein, The binder also contains polyamines and silane coupling agents.

53. The adhesive as claimed in claim 1 or 2, wherein, The adhesive also contains free phosphorus compounds.

54. The adhesive of claim 53, wherein, The free phosphorus-containing compound includes phosphorus-containing oxyacids or their salts or esters, or organophosphorus compounds.

55. The adhesive of claim 53, wherein, The free phosphorus-containing compounds include phosphorus-containing oxyacids. The free phosphorus-containing oxyacids include hypophosphoric acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, or organic phosphoric acid, or their salts or esters.

56. The adhesive of claim 53, wherein, The free phosphorus-containing compounds include organophosphorus compounds. The free organophosphorus compound includes trimethylphosphine, triphenylphosphine, or triphenylphosphine oxide.

57. The adhesive of claim 53, wherein, The content of free phosphorus compounds in the binder is less than 20% by mass relative to 100% by mass of the carboxyl-containing polymer.

58. The adhesive of claim 53, wherein, The content of free phosphorus compounds in the binder is 0.1% to 10% by mass relative to 100% by mass of the carboxyl-containing polymer.

59. The adhesive of claim 53, wherein, The content of free phosphorus compounds in the binder is 0.5% to 7% by mass relative to 100% by mass of the carboxyl-containing polymer.

60. The adhesive as claimed in claim 1 or 2, wherein, The adhesive is an aqueous solution.

61. The adhesive as claimed in claim 1 or 2, wherein, The adhesive contains water. The water content in the adhesive is 10% to 80% by mass relative to 100% of the total amount of adhesive.

62. The adhesive as claimed in claim 1 or 2, wherein, The adhesive contains water. The water content in the adhesive is 20% to 70% by mass relative to 100% of the total amount of adhesive.

63. The adhesive as claimed in claim 1 or 2, wherein, The adhesive contains water. The water content in the adhesive is 25% to 60% by mass relative to 100% of the total amount of adhesive.

64. The adhesive as claimed in claim 1 or 2, wherein, The water content in the adhesive is less than 10% by mass relative to 100% of the total amount of adhesive.

65. The adhesive as claimed in claim 1 or 2, wherein, The water content in the adhesive is less than 5% by mass relative to 100% of the total amount of adhesive.

66. The adhesive as claimed in claim 1 or 2, wherein, The water content in the adhesive is less than 1% by mass relative to 100% of the total amount of adhesive.

67. The adhesive as claimed in claim 1 or 2, wherein, The adhesive has a viscosity of less than 200 mPa·s at 25°C.

68. The adhesive as claimed in claim 1 or 2, wherein, The adhesive has a viscosity of less than 180 mPa·s at 25°C.

69. The adhesive as claimed in claim 1 or 2, wherein, The adhesive has a viscosity of less than 160 mPa·s at 25°C.

70. The adhesive as claimed in claim 1 or 2, wherein, The adhesive has a viscosity of less than 120 mPa·s at 25°C.

71. The adhesive as claimed in claim 1 or 2, wherein, The adhesive has a viscosity of less than 100 mPa·s at 25°C.

72. The adhesive as claimed in claim 1 or 2, wherein, The pH of the adhesive is 1 to 4.

0.

73. The adhesive as claimed in claim 1 or 2, wherein, The pH of the adhesive is 1.5 to 3.

7.

74. The adhesive as claimed in claim 1 or 2, wherein, The pH of the adhesive is 2 to 3.

5.

75. The adhesive as claimed in claim 1 or 2, wherein, The adhesive is a fiber adhesive.

76. A cured body comprising: The cured product of the adhesive as described in claim 1 or 2, and the filler material bonded by the cured product.

77. The cured body as claimed in claim 76, wherein, The filling material includes inorganic fillers.

78. The cured body as claimed in claim 76, wherein, The filling material comprises inorganic fibers or inorganic particles.

79. The cured body as claimed in claim 76, wherein, The filling material comprises inorganic fibers. The inorganic fibers include glass fibers, asbestos, or carbon fibers.

80. The cured body as claimed in claim 76, wherein, The filling material comprises inorganic fibers. The inorganic fiber is a nonwoven fabric.

81. The cured body as claimed in claim 76, wherein, The filler material contains inorganic particles. The inorganic particles include powdered glass, glass particles, or mineral particles.

82. The cured body as claimed in claim 76, wherein, The filling material includes glass wool.

83. The cured body as claimed in claim 76, wherein, The filler material includes organic fillers.

84. The cured body as claimed in claim 76, wherein, The filler material contains organic fibers or organic particles.

85. The cured body as claimed in claim 76, wherein, The filling material contains organic fibers. The organic fibers include wool, cellulose, hemp, nylon, or polyester.

86. The cured body as claimed in claim 76, wherein, The filler material contains organic particles. The organic particles include nylon microparticles or polyester microparticles.

87. A method for manufacturing a cured body, comprising: A process of obtaining a precursor by contacting a carboxyl-containing polymer and a polyol having a weight-average molecular weight of 2000 g / mol to 6000 g / mol with a filler material, wherein the molar ratio of the carboxyl groups in the carboxyl-containing polymer to the polyol in the precursor is 60:40 to 35:65; and The process of curing the precursor. The carboxyl-containing polymer comprises homopolymers containing only structural units derived from acrylic acid. The polyol is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, erythritol, xylitol, and sorbitol.

88. The method for manufacturing a cured body as described in claim 87, wherein, The weight-average molecular weight of the carboxyl-containing polymer is 2500 g / mol to 6000 g / mol.

89. The method for manufacturing a cured body as described in claim 87, wherein, The weight-average molecular weight of the carboxyl-containing polymer is 3000 g / mol to 6000 g / mol.

90. The method for manufacturing a cured body as described in claim 87, wherein, The number-average molecular weight (Mn) of the carboxyl-containing polymer is 1000 g / mol to 4000 g / mol.

91. The method for manufacturing a cured body as described in claim 87, wherein, The number-average molecular weight (Mn) of the carboxyl-containing polymer is 1500 g / mol to 3000 g / mol.

92. The method for manufacturing a cured body as described in claim 87, wherein, The polydispersity (Mw / Mn) of the carboxyl-containing polymer is 1 to 3.

93. The method for manufacturing a cured body as described in claim 87, wherein, The polydispersity (Mw / Mn) of the carboxyl-containing polymer is 1.4 to 2.

5.

94. The method for manufacturing a cured body as described in claim 87, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 80 mol% are COOH groups.

95. The method for manufacturing a cured body as described in claim 87, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 90 mol% are COOH groups.

96. The method for manufacturing a cured body as described in claim 87, wherein, Of the carboxyl groups in the aforementioned carboxyl-containing polymer, more than 95 mol% are COOH groups.

97. The method for manufacturing a cured body as described in claim 87, wherein, The carboxyl-containing polymer contains phosphorus.

98. The method for manufacturing a cured body as described in claim 87, wherein, The carboxyl-containing polymer contains residues derived from phosphorus-containing oxyacids.

99. The method for manufacturing a cured body as described in claim 87, wherein, The carboxyl-containing polymer contains residues of hypophosphoric acid or its salts, phosphorous acid or its salts, phosphoric acid or its salts, pyrophosphoric acid or its salts, polyphosphoric acid or its salts, or organic phosphoric acid or its salts.

100. The method for manufacturing a cured body as described in claim 87, wherein, The polyol comprises a polyol having a viscosity of less than 900 mPa·s at 20°C.

101. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has a viscosity of less than 500 mPa·s at 20°C.

102. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has a viscosity of less than 250 mPa·s at 20°C.

103. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has a viscosity of less than 100 mPa·s at 20°C.

104. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has a viscosity of less than 50 mPa·s at 20°C.

105. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has 2 to 5 hydroxyl groups.

106. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has two or three hydroxyl groups.

107. The method for manufacturing a cured body as described in claim 87, wherein, The polyol has 2 to 5 carbon atoms.

108. The method for manufacturing a cured body as described in claim 87, wherein, The molar ratio of the carboxylic acid group in the carboxyl-containing polymer to the polyol is 60:40 to 40:

60.

109. The method for manufacturing a cured body as described in claim 87, wherein, The precursor also contains polyamines.

110. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine is an amine compound with 4 or more nitrogen atoms per molecule.

111. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine includes polyalkylene polyamine, polyamide polyamine, polyalkylene imine epoxy, or polyethyleneamine.

112. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine comprises polyalkylene polyamines.

113. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine comprises a polymer or copolymer with one or more alkylimines as monomers, or an alkylimine adduct of an aliphatic polyamine.

114. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine comprises a polymer or copolymer of an alkylimine having 2 to 8 carbon atoms.

115. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine comprises a polymer or copolymer of an alkylimine having 2 to 6 carbon atoms.

116. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine comprises a polymer or copolymer of one or more alkylene imides selected from the group consisting of ethylene imide, propylene imide, 1,2-butylene imide, 2,3-butylene imide and 1,1-dimethylethylene imide.

117. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine includes polyethyleneimine.

118. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine is an alkylimine adduct of an aliphatic polyamine obtained by ring-opening addition of alkylimines to 2 to 6 alkylimines.

119. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine is an alkylimine adduct of an aliphatic polyamine obtained by ring-opening addition of alkylimines to 2 to 6 ethylenediamines.

120. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 200 g / mol to 500,000 g / mol.

121. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 250 g / mol to 100,000 g / mol.

122. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 250 g / mol to 80,000 g / mol.

123. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 300 g / mol to 50,000 g / mol.

124. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 400 g / mol to 10000 g / mol.

125. The method for manufacturing a cured body as described in claim 109, wherein, The number-average molecular weight of the polyamine is 500 g / mol to 5000 g / mol.

126. The method for manufacturing a cured body as described in claim 109, wherein, The polyamine does not contain hydroxyl groups.

127. The method for manufacturing a cured body as described in claim 109, wherein, The content of the polyamine in the precursor is 0.01 to 5 parts by mass relative to 100 parts by mass of the combined amount of the carboxyl-containing polymer and the polyol.

128. The method for manufacturing a cured body as described in claim 109, wherein, The content of the polyamine in the precursor is 0.1 to 3 parts by mass relative to 100 parts by mass of the combined amount of the carboxyl-containing polymer and the polyol.

129. The method for manufacturing a cured body as described in claim 87, wherein, The precursor also contains a silane coupling agent.

130. The method for manufacturing a cured body as described in claim 129, wherein, The silane coupling agent comprises an aminosilane coupling agent or an epoxysilane coupling agent.

131. The method for manufacturing a cured body as described in claim 129, wherein, The silane coupling agent comprises γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, or γ-epoxypropoxypropylmethyldimethoxysilane.

132. The method for manufacturing a cured body as described in claim 129, wherein, The content of the silane coupling agent in the precursor is 0.01 to 5 parts by mass relative to the total mass of the carboxyl-containing polymer and the polyol (100 parts by mass).

133. The method for manufacturing a cured body as described in claim 129, wherein, The content of the silane coupling agent in the precursor is 0.1 to 3 parts by mass relative to 100 parts by mass of the total mass of the carboxyl-containing polymer and the polyol.

134. The method for manufacturing a cured body as described in claim 87, wherein, The precursor also contains a polyamine and a silane coupling agent.

135. The method for manufacturing a cured body as described in claim 87, wherein, The precursor also contains free phosphorus-containing compounds.

136. The method for manufacturing a cured body as described in claim 135, wherein, The free phosphorus-containing compound includes phosphorus-containing oxyacids or their salts or esters, or organophosphorus compounds.

137. The method for manufacturing a cured body as described in claim 135, wherein, The free phosphorus-containing compounds include phosphorus-containing oxyacids. The free phosphorus-containing oxyacids include hypophosphoric acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, or organic phosphoric acid, or their salts or esters.

138. The method for manufacturing a cured body as described in claim 135, wherein, The free phosphorus-containing compounds include organophosphorus compounds. The free organophosphorus compound includes trimethylphosphine, triphenylphosphine, or triphenylphosphine oxide.

139. The method for manufacturing a cured body as described in claim 135, wherein, The content of free phosphorus-containing compounds in the precursor is less than 20% by mass relative to 100% by mass of the carboxyl-containing polymer.

140. The method for manufacturing a cured body as described in claim 135, wherein, The content of free phosphorus-containing compounds in the precursor is 0.1% to 10% by mass relative to 100% by mass of the carboxyl-containing polymer.

141. The method for manufacturing a cured body as described in claim 135, wherein, The content of free phosphorus-containing compounds in the precursor is 0.5% to 7% by mass relative to 100% by mass of the carboxyl-containing polymer.

142. The method for manufacturing a cured body as described in claim 87, wherein, The precursor contains a binder. The adhesive comprises: Carboxyl-containing polymers and polyols with a weight-average molecular weight of 2000 g / mol to 6000 g / mol. The molar ratio of the carboxylic acid group in the carboxyl-containing polymer to the polyol is 60:40 to 35:

65. The polyol comprises a polyol having a viscosity of less than 900 mPa·s at 20°C.

143. The method for manufacturing a cured body as described in claim 142, wherein, The content of the carboxyl-containing polymer is 10% to 90% by mass relative to 100% of the total amount of the binder.

144. The method for manufacturing a cured body as described in claim 142, wherein, The content of the carboxyl-containing polymer is 20% to 80% by mass relative to 100% of the total amount of the binder.

145. The method for manufacturing a cured body as described in claim 142, wherein, The content of the polyol in the adhesive is 5% to 60% by mass relative to 100% of the total amount of the adhesive.

146. The method for manufacturing a cured body as described in claim 142, wherein, The content of the polyol in the adhesive is 7% to 50% by mass relative to 100% of the total amount of the adhesive.

147. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive is an aqueous solution.

148. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive contains water. The water content in the adhesive is 10% to 80% by mass relative to 100% of the total amount of adhesive.

149. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive contains water. The water content in the adhesive is 20% to 70% by mass relative to 100% of the total amount of adhesive.

150. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive contains water. The water content in the adhesive is 25% to 60% by mass relative to 100% of the total amount of adhesive.

151. The method for manufacturing a cured body as described in claim 142, wherein, The water content in the adhesive is less than 10% by mass relative to 100% of the total amount of adhesive.

152. The method for manufacturing a cured body as described in claim 142, wherein, The water content in the adhesive is less than 5% by mass relative to 100% of the total amount of adhesive.

153. The method for manufacturing a cured body as described in claim 142, wherein, The water content in the adhesive is less than 1% by mass relative to 100% of the total amount of adhesive.

154. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive has a viscosity of less than 200 mPa·s at 25°C.

155. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive has a viscosity of less than 180 mPa·s at 25°C.

156. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive has a viscosity of less than 160 mPa·s at 25°C.

157. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive has a viscosity of less than 120 mPa·s at 25°C.

158. The method for manufacturing a cured body as described in claim 142, wherein, The adhesive has a viscosity of less than 100 mPa·s at 25°C.

159. The method for manufacturing a cured body as described in claim 142, wherein, The pH of the adhesive is 1 to 4.

0.

160. The method for manufacturing a cured body as described in claim 142, wherein, The pH of the adhesive is 1.5 to 3.

7.

161. The method for manufacturing a cured body as described in claim 142, wherein, The pH of the adhesive is 2 to 3.

5.

162. The method for manufacturing a cured body as described in claim 87, wherein, The filling material includes inorganic fillers.

163. The method for manufacturing a cured body as described in claim 87, wherein, The filling material comprises inorganic fibers or inorganic particles.

164. The method for manufacturing a cured body as described in claim 87, wherein, The filling material comprises inorganic fibers. The inorganic fibers include glass fibers, asbestos, or carbon fibers.

165. The method for manufacturing a cured body as described in claim 87, wherein, The filling material comprises inorganic fibers. The inorganic fiber is a nonwoven fabric.

166. The method for manufacturing a cured body as described in claim 87, wherein, The filler material contains inorganic particles. The inorganic particles include powdered glass, glass particles, or mineral particles.

167. The method for manufacturing a cured body as described in claim 87, wherein, The filling material includes glass wool.

168. The method for manufacturing a cured body as described in claim 87, wherein, The filler material includes organic fillers.

169. The method for manufacturing a cured body as described in claim 87, wherein, The filler material contains organic fibers or organic particles.

170. The method for manufacturing a cured body as described in claim 87, wherein, The filling material contains organic fibers. The organic fibers include wool, cellulose, hemp, nylon, or polyester.

171. The method for manufacturing a cured body as described in claim 87, wherein, The filler material contains organic particles. The organic particles include nylon microparticles or polyester microparticles.

172. The method for manufacturing a cured body as described in claim 142, wherein, The content of the binder in the precursor is 1 to 40 parts by weight relative to 100 parts by weight of filler material, calculated in terms of solid content.

173. The method for manufacturing a cured body as described in claim 142, wherein, The content of the binder in the precursor is 1 to 30 parts by weight relative to 100 parts by weight of filler material, calculated in terms of solid content.

174. The method for manufacturing a cured body as described in claim 142, wherein, The content of the binder in the precursor is 1 to 15 parts by weight relative to 100 parts by weight of filler material, calculated in terms of solid content.

175. The method for manufacturing a cured body as described in claim 87, wherein, The precursor is cured by heating.

176. The method for manufacturing a cured body as described in claim 175, wherein, The heating temperature and heating time are 100℃~300℃ and 1 minute~120 minutes.

177. The method for manufacturing a cured body as described in claim 175, wherein, The heating temperature is 120℃~250℃.

178. The method for manufacturing a cured body as described in claim 175, wherein, The heating temperature is 140℃~230℃.

179. The method for manufacturing a cured body as described in claim 175, wherein, The heating temperature is 150℃~200℃.

180. The method for manufacturing a cured body as described in claim 175, wherein, Heating time is 1 minute to 60 minutes.

181. The method for manufacturing a cured body as described in claim 175, wherein, Heating time is 1 minute to 45 minutes.

182. The method for manufacturing a cured body as described in claim 175, wherein, Heating time is 1 minute to 30 minutes.

183. A cured body formed by curing a precursor, the precursor comprising a filler material and a carboxyl-containing polymer and a polyol having a weight-average molecular weight of 2000 g / mol to 6000 g / mol in contact with the filler material, wherein, The carboxylic acid group in the precursor polymer and the molar ratio of the carboxylic acid group to the polyol are 60:40 to 35:

65. The carboxyl-containing polymer comprises homopolymers containing only structural units derived from acrylic acid. The polyol is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, erythritol, xylitol, and sorbitol.

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