CN114085631B

CN114085631B - Adhesive composition, method for producing the same, and article using the same

Info

Publication number: CN114085631B
Application number: CN202111459398.1A
Authority: CN
Inventors: 杨万泰; 徐灿; 赵长稳; 陈楚轩; 陈冬; 马育红
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2021-12-02
Filing date: 2021-12-02
Publication date: 2023-02-28
Anticipated expiration: 2041-12-02
Also published as: CN114085631A

Abstract

The present invention relates to an adhesive composition, a method of manufacturing the same, and an article using the adhesive composition. The adhesive composition of the present invention comprises: polyol and copolymer a; the copolymer A comprises: structural unit a with amide group and carboxyl group and/or ammonium salt thereof, and structural unit b; the content of the polyol is 10 to 65% by mass based on the total mass of the copolymer A and the polyol.

Description

Adhesive composition, method for producing the same, and article using the same

Technical Field

The present invention relates to an adhesive composition, a method of manufacturing the same, and an article using the adhesive composition.

Background

In the current adhesives, especially the adhesives used for producing artificial boards, the 'trialdehyde glue' (urea formaldehyde resin, phenol formaldehyde resin and melamine formaldehyde resin) prepared by taking formaldehyde as a raw material occupies a larger proportion, which exceeds 80%. The three-aldehyde glue is simple to prepare and low in price, but the board can release free formaldehyde for a long time in the using process, so that the indoor environment is polluted, and the body health of residents is seriously threatened.

The adhesive prepared on the basis of biomass raw materials such as soybean protein, tannin, starch, gelatin and the like does not relate to the use of formaldehyde, but the biomass raw materials have high degradation speed and bring about the problem that the plate is easy to age. Although degradation can be delayed to some extent by the addition of an anti-aging agent, biomass-based adhesives still have problems in terms of cost and resources. This also limits its practical use.

In addition, the production of the board can also be carried out by using polymers such as polyvinyl chloride, high molecular weight polyethylene, chloroprene rubber and the like, but the polymers do not have water solubility, cannot form an aqueous adhesive, can only be mixed with wood raw materials by hot melting or organic solvents, and still have the defects of high cost, energy consumption and environmental pollution.

Therefore, it is important to develop a novel formaldehyde-free artificial board adhesive in view of safety, environmental protection, low production cost, simplicity of application process, durability of finished products, and the like.

For example, patent document 1 proposes an adhesive comprising at least one copolymer having a structural unit having an amide group and a carboxyl group and/or an ammonium salt thereof and other structural units. In addition, patent document 2 provides an adhesive comprising a specific copolymer a having (i) at least one structural unit having an amide group and a carboxyl group and/or an ammonium salt thereof, (ii) at least one structural unit derived from a linear or branched C ₂ -C ₁₈ (ii) a structural unit of an alpha-monoolefin, and (iii) at least one structural unit derived from a monomer having at least two carbon-carbon unsaturated double bonds.

However, various articles, especially wood-based panels, made with these adhesives are deficient in hot water resistance and bond strength.

Patent literature

Patent document 1: CN 112852357A

Patent document 2: CN 112625181A

Disclosure of Invention

Problems to be solved by the invention

In view of the above-mentioned drawbacks in the art, the present invention provides an adhesive composition and a method for manufacturing the same, which is free from formaldehyde emission, low in cost, easy to apply, and improved in hot water resistance and bonding strength of an article made of the adhesive composition. In addition, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide various articles made by using the adhesive composition.

Means for solving the problems

According to the intensive research of the inventor of the present invention, it is found that the technical problems can be solved by implementing the following technical scheme:

[1] an adhesive composition, wherein the adhesive composition comprises: a polyol and a copolymer a;

the copolymer A comprises:

structural unit a having an amide group and a carboxyl group and/or an ammonium salt thereof, and

a structural unit b selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units derived from vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural unit of monoolefin, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from vinyl alkyl ethers of alkyl groups, structural units derived from vinyl pyrrolidone, structural units derived from (meth) acrylonitrile, structural units derived from N-vinylformamide, structural units derived from vinylimidazole, structural units derived from indene compounds, structural units derived from compounds containing a furan ring, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural unit of fraction derived from C ₈ Structural unit of fraction derived from C ₉ Structural units of distillate, structural units derived from coumarone, structural units derived from coal tar light distillate;

wherein the content of the polyol is 10 to 65% by mass based on the total mass of the copolymer A and the polyol.

[2] The adhesive composition according to [1], wherein the polyhydric alcohol is at least one selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound, a phenol compound, a hydroxyl-terminated polyoxyalkylene compound, an alcohol amine compound, glycerin, polyvinyl alcohol, a pentaerythritol compound, a monosaccharide compound, a disaccharide compound and a polysaccharide compound.

[3]According to [1]]Or [2]]The adhesive composition according to (1), wherein in the copolymer a, the structural unit b is selected from at least one of: derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural unit of vinyl alkyl ether of alkyl, structural unit derived from gasoline, structural unit derived from C ₄ Structural units of fractions, derived from C ₅ Structural units of fractions, derived from C ₈ Structural units of fractions, derived from C ₉ Structural units of the distillate, structural units derived from coumarone, structural units derived from coal tar light distillate.

[4] The adhesive composition according to any one of [1] to [3], wherein the content of the structural unit a is 10 to 80 mass% and the content of the structural unit b is 10 to 90 mass% with respect to the total amount of the copolymer A.

[5] The adhesive composition according to any one of [1] to [4], wherein the copolymer A further comprises a structural unit derived from a monomer having at least two non-conjugated carbon-carbon unsaturated double bonds, preferably the non-conjugated carbon-carbon unsaturated double bonds in the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds are selected from the group consisting of a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and non-conjugated carbon-carbon double bonds in a non-conjugated chain diene or a cyclic diene.

[6] The adhesive composition according to any one of [1] to [5], wherein the content of the copolymer A is 3 to 90 mass% and the content of the polyol is 0.4 to 45 mass% with respect to the total amount of the adhesive composition.

[7] The adhesive composition according to any one of [1] to [6], wherein the adhesive composition is in the form of a solution, and the solid content in the adhesive composition is 2 to 40 mass%.

[8] A method for producing an adhesive composition according to any one of [1] to [7], wherein the method comprises: the copolymer B is firstly reacted with ammonia to obtain a copolymer A, and then the copolymer A is mixed with polyalcohol, or the copolymer B is reacted with ammonia in the presence of polyalcohol;

the copolymer B comprises:

structural units a' bearing anhydride groups, and

a structural unit b selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural unit of monoolefin, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from alkyl vinyl alkyl ethers, structural units derived from vinyl pyrrolidones, structural units derived from (meth) acrylonitriles, structural units derived from N-vinylformamides, structural units derived from vinylimidazoles, structural units derived from indene compounds, structural units derived from furan ring-containing compounds, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural units of fractions, derived from C ₈ Structural units of fractions, derived from C ₉ Structural unit of fraction derived from coumaroneStructural units derived from coal tar light ends.

[9] An article comprising a component formed from the adhesive composition according to any one of [1] to [7].

[10] The article according to [9], wherein the article is an artificial board, paper, cloth or paint.

[11] The article according to [9] or [10], wherein the adhesive composition is used in an amount of 1 to 50% by mass in terms of a solid content relative to the total amount of the article.

ADVANTAGEOUS EFFECTS OF INVENTION

Through the implementation of the technical scheme, the invention can obtain the following technical effects:

in the present invention, by using the copolymer a of the present invention and a polyol in combination at a specific ratio, hot water resistance and bonding strength of an article made of the adhesive composition can be significantly improved. In particular, such an effect can be achieved even when another polymer compound capable of participating in curing is not used in the adhesive composition. Furthermore, the adhesive composition of the present invention is free of formaldehyde emissions, low in cost, and easy to apply.

Detailed Description

The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

in the present specification, unless otherwise specified, "alkyl" and "hydroxyalkyl" refer to linear, branched or cyclic "alkyl" and "hydroxyalkyl", respectively, wherein "hydroxyalkyl" refers to an alkyl group substituted with an arbitrary number of hydroxyl groups.

In the present specification, "(meth) acrylonitrile" used includes the meanings of "methacrylonitrile" and "acrylonitrile"; the "(meth) acrylate" used includes the meaning of "methacrylate" as well as "acrylate"; the "(meth) acrylic acid" used includes the meanings of "methacrylic acid" and "acrylic acid"; the term "(meth) acrylamide" as used includes "methacrylamide" as well as "acrylamide".

In the present specification, "curing" is used to mean that, when the adhesive composition is cured, covalent chemical reactions, ionic interactions or clustering, hydrogen bond formation, and the like are caused, thereby causing structural and/or morphological changes to occur within the adhesive composition.

In the present specification, the numerical range represented by the expression "numerical value a to numerical value B" means a range including the end points of numerical values a and B.

In the present specification, the numerical ranges indicated by "above" or "below" refer to numerical ranges including the number.

In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.

In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.

As used herein, "particle diameter" means "average particle diameter" if not specifically stated, and can be measured by a commercially available particle sizer or an electron scanning microscope.

In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

< adhesive composition > <

Adhesive set of the inventionThe compound comprises a polyol and a copolymer A. The copolymer A comprises: structural units a with amide groups and carboxyl groups and/or ammonium salts thereof and structural units b selected from at least one of the following: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from alkyl vinyl alkyl ethers, structural units derived from vinyl pyrrolidones, structural units derived from (meth) acrylonitriles, structural units derived from N-vinylformamides, structural units derived from vinylimidazoles, structural units derived from indene compounds, structural units derived from furan ring-containing compounds, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural units of fractions, derived from C ₈ Structural units of fractions, derived from C ₉ Structural units of the distillate, structural units derived from coumarone, structural units derived from coal tar light distillate. In the present invention, the content of the polyol is 10 to 65% by mass based on the total mass of the copolymer a and the polyol.

In the present invention, by using the copolymer a and the polyol in combination at a specific ratio, moderate crosslinking of the cured copolymer a can be caused to improve both the bonding strength and the hot water resistance. When the content of the polyol is less than 10 mass% with respect to the total mass of the copolymer a and the polyol, the hot water resistance of the produced article (especially, artificial board) is lowered; when the content of the polyol is more than 65% by mass relative to the total mass of the copolymer a and the polyol, the bonding strength of the produced article (especially, artificial board) is reduced.

In the present invention, in some preferred embodiments, the content of the polyol is preferably 10 to 65% by mass, more preferably 12 to 60% by mass, and still more preferably 15 to 55% by mass, relative to the total mass of the copolymer a and the polyol, from the viewpoint of better balance between the bonding strength and the hot water resistance.

As described above, the resulting adhesive composition can satisfy the desired effects of the present invention as long as the content of the polyol is 10 to 65 mass% with respect to the total mass of the copolymer a and the polyol. However, the preferred range of the content of the polyol in the adhesive composition with respect to the total mass of the copolymer a and the polyol is sometimes different for different articles in order to obtain more excellent technical effects.

In some specific embodiments, when the article is a particle board, the content of the polyol is preferably 12 to 60 mass%, more preferably 15 to 58 mass%, relative to the total mass of the copolymer a and the polyol.

In some specific embodiments, when the article is a fiber sheet, the content of the polyol is preferably 10 to 55% by mass, more preferably 12 to 40% by mass, relative to the total mass of the copolymer a and the polyol.

In some specific embodiments, when the article is a plywood, the content of the polyol is preferably from 12 to 60 mass%, more preferably from 20 to 50 mass%, relative to the total mass of the copolymer a and the polyol.

The form of the adhesive composition of the present invention is not particularly limited, and may be in a solid state such as a powder state, a solution state or a dispersion state. Therefore, in the present invention, the content of each of the copolymer a and the polyol with respect to the total amount of the adhesive composition is not particularly limited.

In the present invention, in some preferred embodiments, the content of the above-mentioned copolymer a is preferably 3 to 90% by mass, more preferably 10 to 85% by mass, still more preferably 30 to 80% by mass, and further preferably 35 to 80% by mass, relative to the total amount of the adhesive composition, from the viewpoint of more improving the bonding strength.

In the present invention, in some preferred embodiments, the content of the polyol relative to the total amount of the adhesive composition is preferably 0.4 to 45% by mass, more preferably 1 to 40% by mass, and still more preferably 5 to 30% by mass, from the viewpoint of further achieving both the bonding strength and the hot water resistance.

In some particularly preferred embodiments, the adhesive composition of the invention is in the form of a solution. The solvent used in the solution is not particularly limited, and may be a solvent capable of dissolving each component including the copolymer a and the polyol. In some more preferred embodiments, the solvent is preferably an aqueous solvent comprising at least water. The aqueous solvent may contain, in addition to water, other solvents, for example, alcohol solvents such as methanol and ethanol, polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether, nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone, and the like. In addition, in the case where the binder composition is in the form of a solution, the solid content in the binder composition is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 8 to 25% by mass.

The details of each component in the adhesive composition are described in detail below.

< polyol >

Polyol refers to any compound containing two or more hydroxyl functional groups. In the present invention, there is no particular limitation on the specific kind of the polyol.

In some preferred embodiments, the polyhydric alcohol is preferably at least one selected from the group consisting of aliphatic diol compounds, alicyclic diol compounds, phenolic compounds, hydroxyl-terminated polyoxyalkylene compounds, alcohol amine compounds, glycerin, polyvinyl alcohol, pentaerythritol compounds, monosaccharide compounds, disaccharide compounds, and polysaccharide compounds, from the viewpoint of better obtaining the technical effects of the present invention.

Examples of aliphatic diol compounds include, without limitation, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, and the like. These compounds may be used alone or in combination of two or more.

Examples of alicyclic diol compounds include, without limitation, cyclohexanediol, cyclooctanediol, and the like. These compounds may be used alone or in combination of two or more.

Examples of phenolic compounds include, without limitation, resorcinol, catechol, pyrogallol, and the like. These compounds may be used alone or in combination of two or more.

The hydroxyl-terminated polyoxyalkylene compound is a hydroxyl-terminated compound having at least two (O-R) n structural units in the molecular chain, wherein R is an alkylene group or a hydroxyl-substituted alkylene group, and examples thereof include, but are not limited to, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyglycerol, and the like. These compounds may be used alone or in combination of two or more.

Examples of the alkanolamine compounds include, without limitation, diethanolamine, triethanolamine, ethyldiethanolamine, methyldiethanolamine and the like. These compounds may be used alone or in combination of two or more.

Polyvinyl alcohol is known in the art as a polyvinyl alcohol Consisting of (CH) ₂ -CH (OH)) n (n.gtoreq.2, preferably n.gtoreq.5, more preferably n.gtoreq.10, still more preferably n.gtoreq.15). These compounds may be used alone or in combination of two or more.

Examples of pentaerythritol-based compounds include, without limitation, pentaerythritol, dipentaerythritol, and the like. These compounds may be used alone or in combination of two or more.

Examples of monosaccharide compounds include, without limitation, glucose and fructose, and the like. These compounds may be used alone or in combination of two or more.

Examples of disaccharide based compounds include, without limitation, sucrose and the like. These compounds may be used alone or in combination of two or more.

Examples of polysaccharide compounds include, without limitation, starches of various origins, reduced and/or modified starches, cellulosic compounds, and the like. These compounds may be used alone or in combination of two or more. Here, examples of the cellulose-based compound include, but are not limited to, cellulose, modified cellulose such as hydroxyethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, etc., regenerated cellulose, and the like.

In some more preferred embodiments, the polyol is more preferably at least one selected from the group consisting of aliphatic diol-based compounds, hydroxyl-terminated polyoxyalkylene-based compounds, glycerin, polyvinyl alcohol, pentaerythritol-based compounds, monosaccharide-based compounds, disaccharide-based compounds, and polysaccharide-based compounds.

< copolymer A >

The copolymer A comprises structural units a which carry amide groups and carboxyl groups and/or ammonium salts thereof. In the present invention, the formation mode of the structural unit a is not particularly limited, and in some preferred embodiments, the structural unit a is formed based on the structural unit a' of the copolymer B described below.

In addition, in some preferred embodiments, the content of the structural unit a is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, still more preferably 20 to 65% by mass, and further preferably 35 to 60% by mass, relative to the total amount of the copolymer a.

The copolymer a comprises structural units b selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units derived from vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from compounds having C ₁ ～C ₈ Structural units of alkyl vinyl alkyl ethers, structural units derived from vinylpyrrolidone, structural units derived from (meth) acrylonitrile, structural units derived from N-vinylformamide, structural units derived from vinylimidazoleMeta, structural unit derived from indene compound, structural unit derived from furan ring-containing compound, structural unit derived from gasoline, structural unit derived from C ₄ Structural unit of fraction derived from C ₅ Structural unit of fraction derived from C ₈ Structural units of fractions, derived from C ₉ Structural units of the distillate, structural units derived from coumarone, structural units derived from coal tar light distillate. Here, the expression "derived from" means that the copolymer has a structural unit formed directly or indirectly from a monomer corresponding to the structural unit, as will be understood by those skilled in the art.

Monoethylenically unsaturated C ₃ ～C ₈ Examples of monocarboxylic acids include, without limitation, acrylic acid, methacrylic acid, crotonic acid, and vinyl acetic acid. These monomers may be used alone or in combination of two or more.

Monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Alkyl esters (preferably, monoethylenically unsaturated C) ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₈ Alkyl ester, more preferably, monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₆ Alkyl esters) include, without limitation, C (meth) acrylic acid ₁ ～C ₁₀ Alkyl esters, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. These monomers may be used alone or in combination of two or more.

Monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Hydroxyalkyl esters (preferably, monoethylenically unsaturated C) ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₈ Hydroxyalkyl esters, more preferably monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₆ Hydroxyalkyl esters) include, without limitation, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. These monomers may be used alone or in combination of two or more.

Monoethylenically unsaturated C ₃ ～C ₈ Examples of amides of monocarboxylic acids include, but are not limited to, (meth) acrylamide. These monomers may be used alone or in combination of two or more.

C ₁ ～C ₂₀ Vinyl esters of carboxylic acids (preferably, C) ₂ ～C ₁₈ Vinyl esters of carboxylic acids, more preferably, C ₂ ～C ₁₂ Vinyl esters of carboxylic acids) include, without limitation, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, and the like. These monomers may be used alone or in combination of two or more.

Examples of monovinylarenes include, without limitation, styrene, alpha-methylstyrene, ethylstyrene, o-methylstyrene, p-methylstyrene, vinylnaphthalene, for example. These monomers may be used alone or in combination of two or more.

C ₂ ～C ₂₂ Examples of mono-olefins include, without limitation, C such as ethylene, propylene, n-butene, isobutylene, sec-butene, pentene, 2-methyl-1-butene, 2-methyl-2-butene, and the like ₂ ～C ₂₂ (preferably, C) ₂ ～C ₂₀ More preferably, C ₂ ～C ₁₂ ) An alkene; e.g. cyclopentene, cyclohexene, cycloheptene, etc. C ₃ ～C ₂₂ (preferably, C) ₅ ～C ₂₀ More preferably, C ₅ ～C ₁₂ ) Cyclic alkenes and the like. These monomers may be used alone or in combination of two or more.

C ₄ ～C ₂₂ Conjugated dienes (preferably, C) ₄ ～C ₁₈ Conjugated dienes, more preferably, C ₄ ～C ₁₂ Conjugated dienes) include, without limitation, 1, 3-butadiene, 1, 3-pentadiene, isoprene, 1, 3-hexadiene, cyclopentadiene, methylcyclopentadiene, 1, 3-cyclohexadiene, and the like.

Having a structure of C ₁ ～C ₈ Examples of alkyl vinyl alkyl ethers include, without limitation, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, and2-ethylhexyl vinyl ether. These monomers may be used alone or in combination of two or more.

Examples of indene compounds include, but are not limited to, indene, methylindene, and the like. These monomers may be used alone or in combination of two or more.

Examples of the furan ring-containing compound include, but are not limited to, furan rings selected from C by one or more (e.g., 2 to 4) ₁ ～C ₁₂ Alkyl and C ₁ ～C ₁₂ A monomer substituted with a substituent of hydroxyalkyl group such as furfuryl alcohol, and the furan ring may be further fused with a benzene ring, for example, methylbenzofuran and the like. These monomers may be used alone or in combination of two or more.

In the present invention, gasoline and C ₄ Fraction, C ₅ Fraction, C ₈ Fraction, C ₉ Distillates, coumarone, coal tar light ends are reaction materials which, as known in the art, are used without isolation, and which contain at least one monomer containing a carbon-carbon unsaturated double bond and other substances which do not participate in the polymerization.

Examples of complex monomers from the coal chemical industry include, without limitation, coal tar light fractions and the like. These monomers may be used alone or in combination of two or more.

In some preferred embodiments, structural unit b is preferably selected from at least one of: derived from C ₁ ～C ₂₀ Structural units derived from vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from compounds having C ₁ ～C ₈ Structural unit of vinyl alkyl ether of alkyl, structural unit derived from gasoline, structural unit derived from C ₄ Structural units of fraction, derived from C ₅ Structural unit of fraction derived from C ₈ Structural units of fractions, derived from C ₉ Structural units derived from coumarone, structural units derived from coal tar light ends.

In some preferred embodiments, the content of the structural unit b is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, still more preferably 20 to 70% by mass, relative to the total amount of the copolymer a.

In addition, the copolymer A of the present invention may further contain any other structural unit. For example, in some specific embodiments, copolymer a further comprises structural units derived from monomers having at least two non-conjugated carbon-carbon unsaturated double bonds. In some preferred embodiments, the non-conjugated carbon-carbon unsaturated double bond in the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds is selected from the group consisting of a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and a non-conjugated carbon-carbon double bond in a non-conjugated alkadiene or cyclic diene.

Examples of monomers having at least two non-conjugated carbon-carbon unsaturated double bonds include, without limitation: monomers having at least two (meth) acrylate groups, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like; monomers having at least two (meth) acrylamide groups such as methylenedi (meth) acrylamide, propylenedi (meth) acrylamide, and the like; monomers having at least two vinyl groups, for example, aromatic compounds having at least two vinyl groups such as divinylbenzene, divinyltoluene, trivinylbenzene, and divinylnaphthalene, ethers having at least two vinyl groups such as butanediol divinyl ether and trimethylolpropane trivinyl ether, esters having at least two vinyl groups such as divinyl phthalate, and the like; monomers having at least two allyl groups, for example, aromatic compounds having at least two allyl groups such as diallylbenzene, diallyltoluene, triallylbenzene and diallylnaphthalene, ethers having at least two allyl groups such as butanediol diallyl ether and trimethylolpropane triallyl ether, esters having at least two allyl groups such as diallyl phthalate, and the like; a monomer having at least two non-conjugated carbon-carbon double bonds in a non-conjugated alkadiene or a cyclic diene. These monomers may be used alone or in combination of two or more.

Here, examples of the diene having at least two non-conjugated chains or the cyclic diene include, but are not limited to, 1, 4-pentadiene, 1, 4-hexadiene, 1, 5-hexadiene, 1, 4-cyclohexadiene, 1, 5-cyclooctadiene, dicyclopentadiene, methyldicyclopentadiene, ethyldicyclopentadiene, 5-dimethyldicyclopentadiene and the like.

In some particularly preferred embodiments, the copolymers A of the invention consist exclusively of the structural units a and b described above.

In the present invention, the number average molecular weight of the copolymer a is not particularly limited, and may be any molecular weight suitable for adhesive applications. In some preferred embodiments, the number average molecular weight of copolymer a of the present invention is preferably at least 2000, more preferably at least 5000, still more preferably at least 8000. The upper limit of the molecular weight of the copolymer a is not critical and may be, for example, 500000, or 300000.

In addition, in the case where the copolymer a contains a structural unit derived from a conjugated diene and/or a structural unit derived from a monomer having at least two non-conjugated carbon-carbon unsaturated double bonds, the copolymer a may be crosslinked, and the gel content is preferably 5% to 95%, more preferably 10% to 85%, and still more preferably 20% to 75%.

< other Components >

In the present invention, the binder composition may contain, in addition to the above-mentioned copolymer a and polyol, other components such as an oxygen scavenger, an emulsifier, a filler, a dye, a pigment, an ultraviolet absorber, an antifoaming agent, a leveling agent, an antistatic agent, an antibacterial agent, a crosslinking agent other than polyol, other high molecular compounds other than copolymer a (e.g., polyacrylic copolymer, epoxy resin, natural latex, etc.), and the like, as required. However, in the present invention, in some preferred embodiments, the adhesive composition of the present invention preferably does not contain a polyamidoamine-based copolymer or oligomer or the like, more preferably does not contain other high molecular compounds (including polymers and oligomers) capable of participating in curing, even more preferably other high molecular compounds (including polymers and oligomers) other than the copolymer a, from the viewpoint of ease of manufacturing and improvement of environmental protection properties.

< method for producing adhesive composition >)

The method for producing the adhesive composition of the present invention comprises: the copolymer B is firstly reacted with ammonia to obtain a copolymer A, and then the copolymer A is mixed with polyhydric alcohol, or the copolymer B is reacted with ammonia in the presence of the polyhydric alcohol;

here, "the copolymer B is reacted with ammonia in the presence of a polyol" means that the copolymer B, ammonia, and polyol may be mixed together and reacted, or the copolymer B may be mixed with the polyol first and the resulting mixture may be mixed with ammonia and reacted.

The method for producing the adhesive composition of the present invention will be described in detail below.

In the present invention, the copolymer B contains the structural unit a' having an acid anhydride group. More preferably, the structural unit a' having an acid anhydride group is introduced into the copolymer B by polymerization of a monomer having a carbon-carbon unsaturated double bond and an acid anhydride group. The monomer having a carbon-carbon unsaturated double bond and an acid anhydride group is preferably C ₄ ～C ₈ For example, maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride, etc.

The copolymer B comprises structural units B selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units derived from vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from alkyl vinyl alkyl ethers, structural units derived from vinyl pyrrolidones, structural units derived from (meth) acrylonitriles, structural units derived from N-vinylformamides, structural units derived from vinylimidazoles, structural units derived from indene compounds, structural units derived from furan ring-containing compounds, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural unit of fraction derived from C ₈ Structural units of fractions, derived from C ₉ Structural units of the distillate, structural units derived from coumarone, structural units derived from coal tar light distillate.

The details of the various monomers used to form the structural unit b are as described above and will not be described herein.

In addition, the copolymer B may further comprise any other structural unit, and details of the other structural unit are also as described above and will not be described herein again.

The polymerization method for producing the copolymer B is not particularly limited. Specifically, the polymerization for preparing the copolymer B can be carried out by various conventional polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, interfacial polymerization, and the like. In some preferred embodiments, the polymerization is carried out by precipitation polymerization. Here, the precipitation polymerization may be performed by selecting a solvent capable of dissolving the monomer but incapable of dissolving the resulting copolymer B, but there is no particular limitation on the form of the copolymer B. In some more preferred embodiments, the copolymer B can be obtained directly in powder form by precipitation polymerization.

In some embodiments, the polymerization to prepare copolymer B may be conducted in the presence of a solvent. The solvent may comprise aromatic ether solvent, aromatic hydrocarbon solvent, alkane solvent, ketone solvent, carboxylic ester solvent, or their mixture.

Specific examples of the aromatic ether solvent include: anisole, phenetole, phenylpropane, diphenyl ether. These aromatic ether solvents may be used alone or in combination of two or more.

Specific examples of the aromatic hydrocarbon solvent include: toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, butylbenzene, xylene, diethylbenzene, mesitylene, cyclohexylbenzene, and diphenylethane. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

Specific examples of the alkane solvent include: n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, and the like. These alkane solvents may be used alone or in combination of two or more.

Specific examples of the ketone-based solvent include acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, and the like. These ketone solvents may be used alone or in combination of two or more.

Specific examples of the carboxylic ester solvent include C1 to C ₆ C of carboxylic acids ₁ ～C ₈ Alkyl, phenyl or benzyl esters and C of aromatic carboxylic acids having 6 to 10 carbon atoms ₁ ～C ₈ Alkyl esters and the like, more specifically there may be mentioned ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, isoamyl phenylacetate and the like.

In some specific embodiments, the polymerization to prepare copolymer B may be carried out using an oil-soluble free radical initiator. The oil-soluble radical initiator includes, for example, an azo-type initiator or a peroxide initiator. The azo initiator comprises: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and the like; the peroxide initiator comprises: dibenzoyl peroxide, dicumyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like. The amount of the initiator to be used is 0.05 to 10% by mass, preferably 0.5 to 6% by mass, based on the weight of the monomer.

The polymerization conditions for producing the copolymer B are not particularly limited, and may be appropriately adjusted according to the polymerization method to be actually used. For example, the polymerization reaction may be carried out in the presence of an inert gas such as nitrogen. The polymerization temperature is generally 50 to 120 ℃ and preferably 55 to 100 ℃; the polymerization time is usually 1 to 12 hours, preferably 2 to 8 hours. After the polymerization, the resulting copolymer B may be isolated and dried.

In the present invention, the copolymer B is reacted with ammonia (hereinafter sometimes simply referred to as aminolysis reaction) in the presence or absence of a reaction medium (e.g., an aqueous solvent containing water), thereby obtaining a copolymer a.

In the present invention, ammonia may be involved in the reaction as ammonia gas or in the form of aqueous ammonia as long as the reaction can be carried out, preferably, a desired amination rate can also be achieved. The ammonia concentration in the ammonia water is not particularly limited, and any commercially available product may be used.

The copolymer B may be subjected to the ammonolysis reaction in a solid state (for example, in the form of a powder), in a dispersion (in a dispersion, the copolymer B is in a solid state (for example, in the form of a powder)), or in a solution. In some preferred embodiments, the copolymer B is preferably subjected to the aminolysis reaction in the form of a powder (the copolymer B itself or dispersed in a dispersion medium). In this case, the copolymer B may have a wide range of average particle diameter (several tens of nanometers to several tens of micrometers), more preferably has an average particle diameter of 100nm to 10 μm, still more preferably has an average particle diameter of 150nm to 8 μm, further preferably has an average particle diameter of 200nm to 6 μm, particularly preferably has an average particle diameter of 300nm to 4 μm.

The conditions for the ammonolysis reaction are not particularly limited, and may be appropriately adjusted according to actual needs. For example, the temperature of the ammonolysis reaction is generally less than 100 ℃, preferably from 0 to 80 ℃, and more preferably from 15 to 60 ℃. The time for the aminolysis reaction is usually 2 to 300 minutes, preferably 5 to 120 minutes.

In the present invention, the amination rate after the ammonolysis reaction is 75% or more, and is preferably 90% or more, more preferably 95% or more, from the viewpoint of further improving the water resistance and/or heat resistance of the product. The amination ratio refers to the molar percentage of all the structural units a' in the copolymer B that are formed as the structural units a in the copolymer a, and is generally determined by a titration method.

In some specific embodiments, the reaction product comprising copolymer a obtained by the aminolysis reaction is in the state of a solution or dispersion after the aminolysis reaction, preferably an aqueous composition in the state of a solution or dispersion, more preferably in the form of an aqueous solution or dispersion. Here, the solvent (dispersion medium) other than water to be used is not particularly limited. In some more preferred embodiments, the aqueous solvent comprising water in the aqueous composition may be an aqueous solvent as described for the adhesive composition and will not be described herein again.

More specifically, when the copolymer B is reacted with ammonia in the presence of a polyol (the copolymer B, ammonia, and polyol are mixed together and subjected to an ammonolysis reaction or the copolymer B is mixed with a polyol first and the resulting mixture is mixed with ammonia and subjected to an ammonolysis reaction), the above-mentioned product in a solution state or a dispersion state can be used as a binder composition as it is or after dilution or concentration. When the copolymer B is first mixed and reacted with ammonia, the above-mentioned aminolysis product in a solution state or a dispersion state may be used as a binder composition after mixing with a polyol, directly or after dilution or concentration.

In other specific embodiments, after the aminolysis reaction, the product containing the copolymer a obtained by the aminolysis reaction is in a solid state such as a powder state.

More specifically, when the copolymer B is reacted with ammonia in the presence of a polyol (the copolymer B, ammonia, and polyol are mixed together and subjected to an ammonolysis reaction or the copolymer B is mixed with a polyol first and then mixed with ammonia and subjected to an ammonolysis reaction), the product in a solid state may be used as the adhesive composition as it is or in a state of being dissolved or dispersed in an arbitrary solvent, preferably an aqueous solvent containing water.

When the copolymer B is mixed and reacted with ammonia first, the solid state aminolysis product may be used as the binder composition directly after being mixed with the polyol or in a state of being dissolved or dispersed in an arbitrary solvent, preferably an aqueous solvent containing water, or may be used as the binder composition after being mixed with the polyol in a state of being dissolved or dispersed in an arbitrary solvent, preferably an aqueous solvent containing water.

Here, in some more preferred embodiments, the water-based solvent including water may be as described for the adhesive composition, and is not described herein again.

In the present invention, as described above, the mixing with the polyol may be performed by a method known in the art in the presence or absence of a medium (for example, an aqueous solvent containing water).

In addition, the method for producing the adhesive composition of the present invention may further comprise other steps such as a step of removing a certain (or some) component and/or impurities in the adhesive composition, a step of adding at least one other component to the adhesive composition as needed at any timing, and the like.

< articles comprising Components formed from the adhesive compositions of the present invention > <

In the present invention, articles comprising components formed from the adhesive compositions of the present invention are prepared.

According to the invention, the article is preferably an artificial board, paper, cloth or paint.

The amount of the binder composition used is not particularly limited and may be appropriately adjusted depending on the actual use. In some preferred embodiments, the adhesive composition is used in an amount of preferably 1 to 50% by mass, more preferably 2 to 40% by mass, still more preferably 3 to 35% by mass, further preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass in terms of solid content, relative to the total amount of the article.

In other preferred embodiments, the copolymer a is used in an amount of preferably 1 to 40 mass%, more preferably 2 to 30 mass%, still more preferably 3 to 25 mass%, further preferably 5 to 20 mass%, and particularly preferably 7 to 18 mass%, relative to the total amount of the article.

In some preferred embodiments, the articles of the present invention are wood-based boards formed from lignocellulosic materials and the adhesive compositions of the present invention. The artificial board of the invention is to be understood in a broad sense, i.e. a board formed from any lignocellulosic material and the adhesive composition of the invention. The artificial board of the present invention is not limited to those formed of only wood, but may include boards formed of bamboo, straw, and the like, which are described below. The artificial board of the invention can be various types of artificial boards. In one embodiment, the man-made boards include, but are not limited to, particle board, plywood, fiberboard, density board, straw board, and finger board.

The lignocellulosic material can be derived from a variety of lignocellulosic materials, such as wood, bamboo, bagasse, straw (e.g., wheat straw), flax residue, nut shells, grain hulls, and the like, and mixtures thereof. Wherein the wood comprises various softwoods and/or hardwoods.

Lignocellulosic material may be in the form of sawdust, chaff, wood chips, strands, flakes, fibers, sheets, wood chips, shavings, granules, and the like, as well as combinations of these materials, such as a combination of strands and sawdust.

Lignocellulosic materials can be processed by a variety of conventional techniques. The large wood can be processed into strands in a log flaker. Large pieces of timber and scrap can also be cut into smaller pieces. The large wood can also be flaked in a ring flaker. Large wood is typically debarked prior to flaking.

The size and shape of the lignocellulose material are not particularly limited and may be appropriately used according to actual needs. In some specific embodiments, the size of the lignocellulosic material may be from 1 to 30 mesh, preferably from 2 to 15 mesh. The thickness of the lignocellulose material in the sheet type is not particularly limited, but the thickness of the sheet may be, for example, 0.2mm to 5cm, preferably 1mm to 3cm.

Additionally, in the artificial boards of the invention, in some preferred embodiments, the adhesive composition of the invention preferably fills the gaps between the lignocellulosic materials.

The artificial board of the invention may generally be obtained by various methods known in the art. In some specific embodiments, the man-made boards of the invention may be prepared by a process comprising compressing a mixture of lignocellulosic material and the binder composition of the invention at a temperature of 105 to 300 ℃ and a pressure of 0.4 to 10MPa, preferably for 2 to 60 minutes, more preferably for 3 to 30 minutes, e.g. 5 to 30 minutes. In some preferred embodiments, the pressing is performed at a temperature of 120 to 220 ℃ and/or at a pressure of 1 to 6MPa.

In the pressing, the copolymer A is imidized to generate an acid anhydride group, and the acid anhydride group further reacts with the polyol to increase the crosslinking density. In addition, when the copolymer a has carboxyl groups in the form of their ammonium salts, the ammonium salts of the carboxyl groups are decomposed again into carboxyl groups under the pressing conditions.

The mixture of lignocellulosic material for pressing and the binder composition of the invention may be prepared by mixing lignocellulosic material with the binder composition of the invention. When the binder composition is in a solid state, the binder composition of the present invention may be first dissolved in an aqueous solvent and then mixed with the lignocellulosic material.

In some preferred embodiments, prior to pressing, it is preferred to remove a portion of the moisture in the mixture of lignocellulosic material and binder, for example to reduce the water content of the mixture of lignocellulosic material and binder to less than 30 mass%, preferably less than 25 mass%, for example less than 22 mass%, or less than 18 mass%. The water content of the mixture is generally higher than 5 mass% or higher than 8 mass%. The removal of the water can be carried out by heating, for example, at a temperature of 50 to 90 ℃ and preferably 60 to 80 ℃.

Examples

Examples of the present invention and comparative examples are described in detail below, however, the scope of the present invention is not limited to these examples. In examples and comparative examples, "%" means "% by mass" and "parts" means parts by mass unless otherwise specified.

Example 1: shaving board

Examples 1 to 1

120 parts of C ₉ The fraction, 70 parts of maleic anhydride, 30 parts of styrene, 100 parts of xylene and 3 parts of AIBN were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product is centrifuged, washed and dried to obtain maleic anhydride/C as copolymer B ₉ Fraction/styrene copolymer, the mass percentage of maleic anhydride monomer units in this copolymer B being 46%.

5 parts of the copolymer B,3 parts of aqueous ammonia having a concentration of 37%, 1 part of corn starch and 91 parts of water were stirred at 60 ℃ for 4 hours to obtain a binder composition having a solid content of 6% (the amination rate of the copolymer was 98 mol%; the content of corn starch as a polyol was 1 mass%, the content of the copolymer A was 5 mass% with respect to the total mass of the binder composition; and the content of corn starch as a polyol was 17 mass% with respect to the total mass of the polyol and the copolymer A).

The adhesive composition is mixed with wood shavings (5 mesh to 10 mesh), the amount of the copolymer is 10 parts per 100 parts of wood shavings, and the mixture is uniformly mixed to obtain the premix. The premix was dried at 70 ℃ to a moisture content of 10%.

And (3) putting the premix into a pressing die of 25cm multiplied by 25cm, and carrying out hot pressing at the temperature of 200 ℃, under the pressure of 0.4MPa and for 2 minutes to obtain the shaving board.

Examples 1 to 2

100 parts of C ₈ The distillate, 70 parts of maleic anhydride, 40 parts of styrene, 100 parts of isoamyl acetate and 3 parts of AIBN were mixed and dissolved, and after 20 minutes of nitrogen introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed and dried to obtain maleic anhydride/C as copolymer B ₈ A fraction/styrene copolymer, wherein the mass percentage of the maleic anhydride monomer units in the copolymer B was 47%.

5 parts of the copolymerB. 3 parts of 37% strength aqueous ammonia, 1.5 parts of tapioca starch and 90.5 parts of water were stirred at 60 ℃ for 4 hours to obtain a binder composition having a solid content of 6.5% (copolymer amination 98 mol%; tapioca starch content as polyol 1.5 mass% relative to the total binder composition; maleamic acid/C as copolymer A) ₈ The content of the fraction/styrene copolymer was 5 mass%; the content of tapioca starch as a polyol was 23 mass% with respect to the total mass of the polyol and the copolymer a).

The adhesive composition is mixed with wood shavings (5-10 mesh), the amount of the copolymer is 15 parts per 100 parts of wood shavings, and the mixture is uniformly mixed to obtain the premix. The premix was dried at 70 ℃ to a moisture content of 20%.

And (3) putting the premix into a compression mold of 25cm multiplied by 25cm, and carrying out hot pressing at the temperature of 180 ℃, under the pressure of 0.4MPa and for 3 minutes to obtain the shaving board.

Examples 1 to 3

100 parts of C ₈ The fraction, 70 parts of maleic anhydride, 40 parts of styrene, 100 parts of isoamyl acetate and 3 parts of AIBN were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed and dried to obtain maleic anhydride/C as copolymer B ₈ Fraction/styrene copolymer, the mass percentage of maleic anhydride monomer units in this copolymer B being 47%.

5 parts of the copolymer B,3 parts of 37% aqueous ammonia, 0.6 part of tapioca starch, and 91.4 parts of water were stirred at 60 ℃ for 4 hours to obtain a binder composition having a solid content of 5.6% (the amination ratio of the copolymer was 98 mol%; the tapioca starch content as a polyhydric alcohol was 0.6 mass% relative to the total amount of the binder composition; maleic acid amide/C as a copolymer A) ₈ The content of the fraction/styrene copolymer was 5 mass%; the content of tapioca starch as a polyol was 10.7 mass% with respect to the total mass of the polyol and the copolymer a).

Examples 1 to 4

5 parts of the copolymer B,3 parts of aqueous ammonia having a concentration of 37%, 8.5 parts of tapioca starch and 83.5 parts of water were stirred at 60 ℃ for 4 hours to obtain an adhesive composition having a solid content of 13.5% (amination: 98 mol% of copolymer; tapioca starch content as a polyhydric alcohol is 8.5% by mass relative to the total amount of adhesive composition; maleamic acid/C as a copolymer A ₈ The content of the fraction/styrene copolymer was 5 mass%; the content of tapioca starch as a polyol was 63 mass% with respect to the total mass of the polyol and the copolymer a).

And (3) putting the premix into a die with the size of 25cm multiplied by 25cm, and carrying out hot pressing at the temperature of 180 ℃, under the pressure of 0.4MPa and for 3 minutes to obtain the shaving board.

Examples 1 to 5

10 parts of vinyl acetate, 11.5 parts of maleic anhydride, 0.225 part of divinylbenzene, 300 parts of isoamyl acetate and 0.2 part of AIBN were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed and dried to obtain a maleic anhydride/vinyl acetate/divinylbenzene copolymer as a white powder as copolymer B having a mass percentage of maleic anhydride monomer units of 52%.

15 parts of the copolymer B,6 parts of 37% aqueous ammonia, 6 parts of sucrose, and 79 parts of water were stirred at room temperature for 4 hours to obtain a binder composition having a solid content concentration of 20.7% (the amination ratio of the copolymer was 99 mol%; the content of sucrose as a polyol was 5.7% by mass, the content of maleamic acid/vinyl acetate/divinylbenzene copolymer as the copolymer A was 14% by mass, and the content of sucrose as a polyol was 29% by mass, based on the total mass of the polyol and the copolymer A).

The adhesive composition is mixed with poplar wood shavings (5 meshes-10 meshes, water content 5%) and the amount of the copolymer in each 100 parts of the shavings is 8 parts, and the mixture is uniformly mixed to obtain the premix. The premix was dried at 70 ℃ to remove water to a water content of 15%.

Placing the premix in a compression mold of 25cm × 25cm × 3cm, and hot pressing at 180 deg.C under 0.4MPa for 10 min to obtain shaving board with thickness of 3 mm.

Examples 1 to 6

120 portions of C ₉ The distillate, 40 parts of maleic anhydride, 100 parts of xylene and 4 parts of Azobisisobutyronitrile (AIBN) were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to give maleic anhydride/C as copolymer B in the form of a white powder ₉ A copolymer fraction wherein the mass percentage of the maleic anhydride monomer units in the copolymer B was 46%.

15 parts of the copolymer B,6 parts of 37% aqueous ammonia and 79 parts of water were stirred at room temperature for 4 hours to obtain maleamic acid/C as a copolymer A having a solid content of 15% ₉ The copolymer was distilled (amination 98 mol% of copolymer) to give a viscous liquid.

100 parts of this viscous liquid and 20 parts of glycerin were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 29% (based on the total amount of the binder composition, the content of glycerin as a polyol was 16.7 mass%, the content of copolymer a was 12.5 mass%, and the content of glycerin as a polyol was 57 mass% based on the total mass of the polyol and copolymer a).

Placing the premix in a compression mold of 25cm × 25cm × 3cm, and hot-pressing at 200 deg.C under 0.4MPa for 10 min to obtain a shaving board with a thickness of 3 mm.

Comparative examples 1 to 1

5 parts of the copolymer B,3 parts of 37% strength aqueous ammonia and 92 parts of water were stirred at 60 ℃ for 4 hours to obtain a mixture containing maleic amide acid/C as the copolymer A ₈ Fraction/styrene copolymer binder composition having a solids content of 5% (98 mol% amination of the copolymer).

The density of the pressed particle board was measured and the pressed particle board was tested for water pick-up thickness swell (2 h and 24 h) and hot water resistance (internal bond strength before and after boiling water test) according to GB/T4897-2015, respectively. The results obtained are shown in table 1.

TABLE 1

According to the national standard GB/T4897-2015, the expansion rate of the furniture shaving board used in a wet state for 2 hours is required to be lower than 8%, and the expansion rate for 24 hours is required to be lower than 23%; the internal bonding strength is higher than 0.45, and the strength after boiling water experiments is higher than 0.09. The properties of the particle boards obtained in examples 1-1 to 1-6 of the present invention were superior to the national standard, as listed in table 1, except that comparative example 1-1 did not satisfy the national standard.

Example 2: fiber board

Example 2-1

30 parts of styrene, 30 parts of maleic anhydride, 3 parts of divinylbenzene, 100 parts of isoamyl acetate and 0.5 part of AIBN were mixed and dissolved, and after 20 minutes of nitrogen introduction, precipitation polymerization was carried out at 70 ℃ for 2 hours. The product was centrifuged, washed and dried to obtain a maleic anhydride/styrene/divinylbenzene copolymer as a copolymer B in which the mass percentage of the maleic anhydride monomer units was 48%.

5 parts of the copolymer B,3 parts of aqueous ammonia having a concentration of 37%, 1 part of corn starch and 91 parts of water were stirred at 60 ℃ for 4 hours to obtain a binder composition having a solid content of 6% (the amination rate of the copolymer was 99 mol%, the content of corn starch as a polyol was 1% by mass, the content of maleamic acid/styrene/divinylbenzene copolymer as the copolymer A was 5% by mass, and the content of corn starch as a polyol was 16.7% by mass based on the total mass of the copolymer A and the polyol).

The adhesive composition was mixed with poplar fibers (20 mesh), the amount of the above copolymer was 10 parts per 100 parts of the fibers, and the mixture was mixed uniformly to obtain a premix. The premix was dried at 70 ℃ to a moisture content of 15%.

And (3) putting the premix into a die with the size of 25cm multiplied by 25cm, and carrying out hot pressing at the temperature of 200 ℃, under the pressure of 0.3MPa and for 2 minutes to obtain the fiberboard.

Examples 2 to 2

120 parts of C ₉ Fraction, 60 parts of maleic anhydride, 20 parts ofStyrene, 100 parts of xylene and 2 parts of AIBN were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed and dried to obtain maleic anhydride/C as copolymer B ₉ Fraction/styrene copolymer, the mass percentage of maleic anhydride monomer units in this copolymer B being 46%.

5 parts of the copolymer B,3 parts of aqueous ammonia having a concentration of 37%, 0.6 part of tapioca starch, and 91.4 parts of water were stirred at 60 ℃ for 4 hours to obtain a binder composition having a solid content of 5.5% (amination ratio of copolymer 98 mol%, tapioca starch content as polyol 0.6 mass% relative to the total binder composition, maleamic acid/C as copolymer A) ₉ The content of the fraction/styrene copolymer was 5 mass%; the content of tapioca starch as a polyol was 10.7 mass% with respect to the total mass of the copolymer a and the polyol).

The adhesive composition was mixed with poplar fibers (20 mesh) in an amount of 15 parts per 100 parts of the fibers, and the mixture was mixed uniformly to obtain a premix. The premix was dried at 70 ℃ to a moisture content of 15%.

And (3) putting the premix into a compression mold of 25cm multiplied by 25cm, and carrying out hot pressing at the temperature of 200 ℃, under the pressure of 0.3MPa and for 2 minutes to obtain the fiberboard.

Examples 2 to 3

100 parts of C ₈ The fractions, 30 parts of maleic anhydride, 100 parts of xylene and 2 parts of dibenzoyl peroxide (BPO) were dissolved in a mixture, and after 20 minutes of nitrogen introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to give maleic anhydride/C as copolymer B in the form of a white powder ₈ A copolymer (weight-average molecular weight: 45000) was prepared by mixing a copolymer B containing a maleic anhydride monomer unit in an amount of 46% by mass.

15 parts of the copolymer B, 7.5 parts of 37% aqueous ammonia and 77.5 parts of water were stirred at room temperature for 4 hours to obtain maleamic acid/C as a copolymer A having a solid content of 15% ₈ The copolymer was distilled (amination 99 mol% of copolymer) to give a viscous liquid.

100 parts of the viscous liquidStirred with 6 parts of sucrose at room temperature for 5 minutes to obtain a binder composition having a solid content of 18.27% (the content of sucrose as a polyol is 5.7% by mass relative to the total amount of the binder composition, maleamic acid/C as copolymer A ₈ The content of the distillate copolymer was 14 mass%; the content of sucrose as a polyol was 29 mass% with respect to the total mass of the copolymer a and the polyol).

The adhesive composition is mixed with poplar fiber (20 meshes, water content 9%) with the amount of copolymer being 8 parts per 100 parts of fiber, and the mixture is uniformly mixed to obtain a premix. The premix was dried at 70 ℃ to remove water to a water content of 15%.

Placing the premix in a compression mold of 25cm × 25cm × 3cm, and hot-pressing at 180 deg.C under 0.4MPa for 10 min to obtain a fiber board with a thickness of 3 mm.

The density of the pressed fiber board was measured, and the pressed fiber board was subjected to a water absorption thickness expansion ratio (24 h) and hot water resistance (internal bonding strength before and after boiling water test) according to GB/T11718-2009. The results obtained are shown in table 2.

TABLE 2

According to the national standard GB/T11718-2009, the 24h expansion rate of the furniture type medium-density fiberboard used in a wet state is required to be lower than 32%, the internal bonding strength is required to be more than 0.6, and the internal bonding strength is required to be more than 0.2 after a boiling water experiment. The properties of the fiber boards listed in table 2 are superior to the national standard requirements.

Example 3: plywood board

Example 3-1

12.8 parts of styrene, 12.25 parts of maleic anhydride, 150 parts of isoamyl acetate and 0.5 part of BPO were mixed and dissolved, and after introducing nitrogen gas for 20 minutes, precipitation polymerization was carried out at 90 ℃ under a pressure of 0.4MPa for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to obtain a maleic anhydride/styrene copolymer as a copolymer B in the form of a white powder, the mass percentage of the maleic anhydride monomer units in the copolymer B being 48%.

15 parts of the copolymer B, 7.5 parts of 37% strength aqueous ammonia and 77.5 parts of water were stirred at room temperature for 4 hours to obtain a maleamic acid/styrene copolymer (amination 99 mol%) viscous liquid as the copolymer A having a solid content of 15%.

100 parts of this viscous liquid and 7.5 parts of corn starch were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 20.93% (the content of corn starch as a polyol was 7 mass%, the content of the maleamic acid/styrene copolymer of the copolymer a was 13.9 mass%, and the content of corn starch as a polyol was 33 mass% with respect to the total mass of the copolymer a and the polyol).

The adhesive composition was coated on a basswood veneer having a water content of 12% and a size of 160mm × 160mm × 1.5mm in an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 135 ℃ for 1MPa for 40 minutes to obtain the three-layer plywood. The bond strength of the plywood was measured to be 1.06MPa according to GB/T9846-2015.

Examples 3 to 2

100 parts of this viscous liquid and 10 parts of industrial flour were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 20% (the content of industrial flour as polyol was 9% by mass, the content of maleamic acid/styrene copolymer as copolymer a was 13.6% by mass, and the content of industrial flour as polyol was 40% by mass, relative to the total mass of copolymer a and polyol).

The adhesive composition was coated on a basswood veneer having a water content of 12% and a size of 160mm × 160mm × 1.5mm in an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 135 ℃ for 1MPa for 40 minutes to obtain the three-layer plywood. The plywood was measured to have a bond strength of 0.82MPa according to GB/T9846-2015.

Examples 3 to 3

12.8 parts of styrene, 12.25 parts of maleic anhydride, 150 parts of isoamyl acetate and 0.5 part of BPO were mixed and dissolved, and after introducing nitrogen gas into the system for 20 minutes, precipitation polymerization was carried out at 90 ℃ under a pressure of 0.4MPa for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to obtain a maleic anhydride/styrene copolymer in the form of a white powder as copolymer B in which the percentage by mass of the maleic anhydride monomer units was 48%.

100 parts of this viscous liquid and 12.5 parts of corn starch were mixed and stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 24.44% (based on the total amount of the binder composition, the content of corn starch as a polyol was 11 mass%, the content of a maleamic acid/styrene copolymer as a copolymer a was 13.3 mass%, and the content of corn starch as a polyol was 45 mass% based on the total mass of the copolymer a and the polyol).

Combining the adhesiveCoating the product on poplar veneer with water content of 12% and size of 160mm × 160mm × 1.5mm, wherein the average coating amount is 90g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 135 ℃ for 1MPa for 40 minutes to obtain the three-layer plywood. The plywood was measured to have a bond strength of 0.79MPa according to GB/T9846-2015.

Examples 3 to 4

100 parts of C ₈ The fractions, 30 parts of maleic anhydride, 100 parts of xylene and 2 parts of dibenzoyl peroxide (BPO) were dissolved in a mixture, and after 20 minutes of nitrogen introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to give maleic anhydride/C as copolymer B in the form of a white powder ₈ A copolymer (weight average molecular weight: 45000) was prepared by mixing a copolymer B containing maleic anhydride monomer units in an amount of 46% by mass.

15 parts of the copolymer B, 7.5 parts of 37% aqueous ammonia and 77.5 parts of water were stirred at room temperature for 4 hours to obtain maleamic acid/C as a copolymer A having a solid content of 15% ₈ The copolymer fraction (amination 99 mol%) was viscous.

100 parts of this viscous liquid and 6 parts of sucrose were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 19.81% (the content of sucrose as a polyol was 5.7% by mass relative to the total amount of the binder composition, and maleamic acid/C as copolymer A ₈ The content of the distillate copolymer was 14 mass%; the content of sucrose as a polyol was 29 mass% with respect to the total mass of the copolymer a and the polyol).

The adhesive composition was coated on basswood veneers having a water content of 12% and sizes of 160mm x 1.5mm at an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 145 ℃ for 1MPa for 30 minutes to obtain the three-layer plywood. The bond strength of the plywood was measured to be 1.15MPa according to GB/T9846-2015.

Examples 3 to 5

15 parts of the copolymer B, 7.5 parts of 37% aqueous ammonia and 77.5 parts of water were stirred at room temperature for 4 hours to obtain maleamic acid/C as a copolymer A having a solid content of 15% ₉ The copolymer fraction (amination 98 mol%) was viscous.

100 parts of this viscous liquid and 6 parts of sucrose were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 19.81% (5.7% by mass of sucrose as a polyol based on the total amount of the binder composition; maleamic acid/C as a copolymer A) ₉ The content of the distillate copolymer was 14 mass%; the content of sucrose as a polyol was 29 mass% with respect to the total mass of the copolymer a and the polyol).

The adhesive composition was coated on a basswood veneer having a water content of 12% and a size of 160mm × 160mm × 1.5mm in an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 145 ℃ for 1MPa for 30 minutes to obtain the three-layer plywood. The plywood was measured to have a bond strength of 1.09MPa according to GB/T9846-2015.

Comparative example 3-1

120 parts of C ₉ The fraction, 40 parts of maleic anhydride, 100 parts of xylene and 4 parts of Azobisisobutyronitrile (AIBN) were mixed and dissolved, and after 20 minutes of nitrogen gas introduction, precipitation polymerization was carried out at 70 ℃ for 6 hours. The product was centrifuged and washed three times with petroleum etherDrying to give maleic anhydride/C as copolymer B in the form of a white powder ₉ A copolymer fraction wherein the mass percentage of the maleic anhydride monomer units in the copolymer B was 46%.

The viscous liquid is directly used as adhesive composition to be coated on basswood veneer with water content of 12% and size of 160mm × 160mm × 1.5mm, and average coating amount is 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 145 ℃ for 1MPa for 30 minutes to obtain the three-layer plywood. The plywood test pieces were tested for bond strength according to GB/T9846-2015 and failed to open.

Comparative examples 3 to 2

12.8 parts of styrene, 12.25 parts of maleic anhydride, 150 parts of isoamyl acetate and 0.5 part of BPO were mixed and dissolved, and after introducing nitrogen gas for 20 minutes, precipitation polymerization was carried out at 90 ℃ under a pressure of 0.4MPa for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to obtain a maleic anhydride/styrene copolymer in the form of a white powder as copolymer B in which the percentage by mass of the maleic anhydride monomer units was 48%.

100 parts of this viscous liquid and 1 part of corn starch were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 15.84% (based on the total amount of the binder composition, the content of corn starch as a polyol was 1 mass%, the content of maleamic acid/styrene copolymer as copolymer a was 15 mass%, and the content of corn starch as a polyol was 6 mass% based on the total mass of copolymer a and polyol).

The adhesive composition was coated on basswood veneers having a water content of 12% and sizes of 160mm x 1.5mm at an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, placing the blanks under a double-flat-plate hot press for pressing, performing cold pressing at room temperature in advance at the pressure of 1MPa for 1 hour, and performing hot pressing at the hot pressing temperature of 135 ℃ for 1MPa for 40 minutes to obtain the three-layer plywood. The plywood test pieces were tested for bond strength according to GB/T9846-2015 and failed to open.

Comparative examples 3 to 3

12.8 parts of styrene, 12.25 parts of maleic anhydride, 150 parts of isoamyl acetate and 0.5 part of BPO were mixed and dissolved, and after introducing nitrogen gas for 20 minutes, precipitation polymerization was carried out at 90 ℃ under a pressure of 0.4MPa for 6 hours. The product was centrifuged, washed three times with petroleum ether and dried to obtain the maleic anhydride/styrene copolymer as copolymer B in the form of a white powder.

100 parts of this viscous liquid and 35 parts of corn starch were stirred at room temperature for 5 minutes to obtain a binder composition having a solid content of 37% (based on the total amount of the binder composition, the content of corn starch as a polyol was 26 mass%, the content of maleamic acid/styrene copolymer as copolymer a was 11 mass%, and the content of corn starch as a polyol was 70 mass% based on the total mass of copolymer a and polyol).

The adhesive composition was coated on basswood veneers having a water content of 12% and sizes of 160mm x 1.5mm at an average coating amount of 50g/m ² Assembling blanks according to the cross grain-vertical grain-cross grain direction, pressing under a double-flat plate hot press, pre-cold pressing at room temperature, 1MPa for 1 hour, and hot pressing at 135 deg.CThe force is 1MPa, and the hot pressing time is 40 minutes, so that the three-layer plywood is obtained. The bonding strength of the plywood measured according to GB/T9846-2015 is 0.61MPa, which is lower than 0.7MPa required by the national standard.

Claims

1. An adhesive composition, characterized in that the adhesive composition comprises: a polyol and a copolymer a;

the copolymer A comprises:

a structural unit b selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from alkyl vinyl alkyl ethers, structural units derived from vinyl pyrrolidones, structural units derived from (meth) acrylonitriles, structural units derived from N-vinylformamides, structural units derived from vinylimidazoles, structural units derived from indene compounds, structural units derived from furan ring-containing compounds, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural unit of fraction derived from C ₈ Structural units of fractions, derived from C ₉ A structural unit of a fraction, a structural unit derived from coumarone, a structural unit derived from a coal tar light fraction;

the polyhydric alcohol is at least one selected from glycerol, starch, reduced and/or modified starch;

wherein the content of the polyol is 10 to 65% by mass with respect to the total mass of the copolymer A and the polyol.

2. The adhesive composition according to claim 1, wherein in the copolymer a, the structural unit b is selected from at least one of: derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural unit of monoolefin, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural unit of vinyl alkyl ether of alkyl, structural unit derived from gasoline, structural unit derived from C ₄ Structural unit of fraction derived from C ₅ Structural unit of fraction derived from C ₈ Structural unit of fraction derived from C ₉ Structural units of the distillate, structural units derived from coumarone, structural units derived from coal tar light distillate.

3. The adhesive composition according to claim 1 or 2, wherein the content of the structural unit a is 10 to 80% by mass and the content of the structural unit b is 10 to 90% by mass based on the total amount of the copolymer a.

4. Adhesive composition according to claim 1 or 2, characterized in that the copolymer a further comprises structural units derived from monomers having at least two non-conjugated carbon-carbon unsaturated double bonds selected from the group consisting of (meth) acrylate groups, (meth) acrylamide groups, vinyl groups, allyl groups and non-conjugated carbon-carbon double bonds in non-conjugated alkadienes or cyclodienes.

5. The adhesive composition according to claim 1 or 2, wherein the content of the copolymer a is 3 to 90% by mass and the content of the polyol is 0.4 to 45% by mass, based on the total amount of the adhesive composition.

6. The adhesive composition according to claim 1 or 2, wherein the adhesive composition is in the form of a solution, and the solid content in the adhesive composition is 2 to 40 mass%.

7. A method for producing the adhesive composition according to any one of claims 1 to 6, characterized in that the method comprises: the copolymer B is firstly reacted with ammonia to obtain a copolymer A, and then the copolymer A is mixed with polyalcohol, or the copolymer B is reacted with ammonia in the presence of polyalcohol;

the copolymer B comprises:

structural units a' bearing anhydride groups, and

a structural unit b selected from at least one of: from monoethylenically unsaturated C ₃ ～C ₈ Structural units of monocarboxylic acids, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of alkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ C of monocarboxylic acids ₁ ～C ₁₀ Structural units of hydroxyalkyl esters, derived from monoethylenically unsaturated C ₃ ～C ₈ Structural unit of amide of monocarboxylic acid, derived from C ₁ ～C ₂₀ Structural units of vinyl esters of carboxylic acids, structural units derived from monovinylarenes, structural units derived from C ₂ ～C ₂₂ Structural units of monoolefins, derived from C ₄ ～C ₂₂ Structural unit of conjugated diene derived from diene having C ₁ ～C ₈ Structural units derived from alkyl vinyl alkyl ethers, structural units derived from vinyl pyrrolidones, structural units derived from (meth) acrylonitriles, structural units derived from N-vinylformamides, structural units derived from vinylimidazoles, structural units derived from indene compounds, structural units derived from furan ring-containing compounds, structural units derived from gasoline, structural units derived from C ₄ Structural units of fractions, derived from C ₅ Structural units of fractions, derived from C ₈ Structural units of fractions, derived from C ₉ Structural unit of distillateA structural unit derived from coumarone, and a structural unit derived from a coal tar light fraction.

8. An article comprising a component formed from the adhesive composition according to any one of claims 1-6.

9. The article of claim 8, wherein the article is an artificial board, paper, cloth, or paint.

10. The article according to claim 8 or 9, characterized in that the binder composition is used in an amount of 1 to 50 mass% in terms of solid content, relative to the total amount of the article.