JP2015120839A - adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive that uses a resin derived from biomass as a raw material and is excellent in not only heat fusibility but also durability and to provide an excrement- treating agent for a pet that is produced by using the adhesive.SOLUTION: The adhesive comprises a resin. The resin is produced by subjecting a dicarboxylic acid component including a dicarboxylic acid compound having a furan ring and a diol and/or a diamine to condensation, has a content of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component exceeding 90 mol%, and has a melting point of not less than 50°C to not more than 200°C. The excrement-treating agent for a pet is produced by extrusion molding the adhesive and a pulverized product of a woody material at a temperature equal to or higher than the melting point of the resin contained in the adhesive. An adhesion method comprises adhering using the resin.

Description

  The present invention relates to an adhesive excellent in heat-fusibility and durability. Furthermore, this invention relates to the excrement disposal agent for pets. The invention further relates to a bonding method.

  In recent years, as environmentally friendly materials, resins using biomass-derived raw materials and resins having biodegradability have been developed and put into practical use. Patent document 1 has a furan structure and a reduced viscosity (ηsp) with the object of providing a thermoplastic resin having a sufficient molecular weight that is excellent in heat resistance, mechanical properties, and weather resistance using biomass as a raw material. A thermoplastic resin having a / C) of 0.48 dL / g or more and a terminal acid value of less than 200 μeq / g is disclosed.

  Patent Document 2 discloses a biodegradation characterized in that it is derived from the polyfunctional aromatic acid containing units derived from at least one diol, at least one aliphatic dicarboxylic acid and at least two polyfunctional aromatic acids. Aliphatic aliphatic-aromatic polyesters are disclosed.

  Patent Document 3 discloses a pet excreta treatment material using a pulverized material derived from a plant as a main constituent substrate, and 1) 70 to 99.99% by mass of a pulverized material derived from a plant and 2) A pet excreta treating material containing 1 to 20% by mass of a synthetic resin and 3) 0.01 to 5% by mass of tectosilicate is described.

JP 2008-291243 A Special table 2013-510213 gazette JP 2006-345830 A

  However, an adhesive produced using, for example, polylactic acid (PLA) as a biomass-derived polyester resin has poor durability, for example, hydrolysis resistance. Therefore, such an adhesive is difficult to use as an adhesive for producing a pet excrement treating agent such as cat sand as disclosed in Patent Document 3, for example, where hydrolysis resistance is required. It was.

  Further, in Patent Document 2, although there is a description that a resin may be used as a pressure-sensitive adhesive, when the resin is used as an adhesive for a pet excrement treating agent, the durability is poor.

  Accordingly, an object of the present invention is to provide an adhesive that uses a biomass-derived resin as a raw material, and has excellent durability as well as heat-fusibility. Furthermore, the subject of this invention is providing the excrement disposal agent for pets obtained using this adhesive agent.

That is, the gist of the present invention is as follows.
[1] An adhesive containing a resin,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. An adhesive which is a resin exceeding mol%, and the melting point of the resin is 50 ° C. or higher and 200 ° C. or lower;
[2] Pet excreta treating agent obtained by extruding the adhesive according to [1] and a pulverized material of a wood material at a temperature equal to or higher than the melting point of the resin in the adhesive; and [3 A resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or a diamine, wherein the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component exceeds 90 mol%. In addition, the present invention relates to an adhesion method in which the resin has a melting point of 50 ° C. or higher and 200 ° C. or lower.

  The adhesive of the present invention exhibits not only heat-fusibility but also excellent durability.

  In the present invention, it has been found that by using a flanged carboxylic acid compound in excess of 90 mol% in the dicarboxylic acid component, a resin excellent in durability as well as heat-fusibility can be obtained. This is because, unlike benzene ring resins, furan ring resins are highly polar, so they easily adhere to the target agent, and the furan ring is also excellent in hydrolysis resistance after storage. Conceivable.

  Even in the resin disclosed in Patent Document 2, furan carboxylic acid is used as an acid component constituting the resin, but it is considered that sufficient durability was not exhibited due to the small amount of furan carboxylic acid. .

The present invention is an adhesive containing a resin,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. It is an adhesive having a melting point of 50 ° C. or higher and 200 ° C. or lower.

  The resin in the present invention is not particularly limited as long as it is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, but the specific resin used in the present invention is not limited. Examples of the resin include condensation polymers such as polyester, polyamide, and polyester carbonate. Among them, polyester and polyamide are suitable resins.

  Hereafter, each component used for manufacture of resin of this invention is demonstrated.

[Dicarboxylic acid component (hereinafter also simply referred to as acid component)]
From the viewpoint of durability of the adhesive, the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component used as a raw material for the resin is more than 90 mol%, preferably 93 mol% or more, more preferably 95 mol% or more. More preferably, it is 98 mol% or more, still more preferably 99 mol% or more, substantially more preferably 100%.

  The dicarboxylic acid compound having a furan ring may be a petroleum-derived raw material or a biomass-derived raw material, but it is preferable to use a biomass-derived raw material. In addition, the component as used in this invention is synonymous with a raw material.

  Examples of the dicarboxylic acid compound having a furan ring include furan-2,5-dicarboxylic acid (also referred to as 2,5-furandicarboxylic acid), furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid, A furan carboxylic acid compound such as furan-3,4-dicarboxylic acid can be used, and furan-2,5-dicarboxylic acid is preferable from the viewpoint of heat fusion property and durability of the resulting adhesive.

  As the dicarboxylic acid compound having a furan ring, only one component may be used, or a plurality of components may be used in combination. In the present specification, the “carboxylic acid compound” includes not only a carboxylic acid but also an ester of the carboxylic acid and an alcohol having 1 to 3 carbon atoms, and an acid anhydride of the carboxylic acid.

  The acid component may contain a carboxylic acid compound other than the dicarboxylic acid compound having a furan ring as long as the effects of the present invention are not impaired. Examples of such carboxylic acid compounds include aliphatic dicarboxylic acid compounds. The aliphatic dicarboxylic acid compound is more preferably a linear aliphatic dicarboxylic acid from the viewpoint of the heat-fusibility of the resulting resin. As the aliphatic dicarboxylic acid compound, only one component may be used or a plurality of components may be used in combination.

  The aliphatic dicarboxylic acid compound is preferably a fatty acid having 2 or more carbon atoms, more preferably 6 or more from the viewpoint of heat-fusibility, and preferably 12 or less, more preferably 10 or less from the viewpoint of durability. Group dicarboxylic acid compounds. Specifically, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and acid anhydrides thereof (1 to 1 carbon atoms) 3) alkyl esters and the like.

  The aliphatic dicarboxylic acid compound is preferably less than 10 mol%, more preferably 7 mol% or less, still more preferably 5 mol% or less, and still more preferably, in the dicarboxylic acid component, from the viewpoint of durability of the produced adhesive. Is 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol%.

  Other acid components include aromatic dicarboxylic acid compounds such as terephthalic acid. These aromatic carboxylic acid compounds are preferably 5 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol% in the acid component from the viewpoint of heat-fusibility.

  Further, an acid not included in the dicarboxylic acid, for example, an aromatic tricarboxylic acid compound such as trimellitic acid may be used together with the dicarboxylic acid. The aromatic tricarboxylic acid compound is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, more preferably 5 mol, based on 100 mol% of the dicarboxylic acid component, from the viewpoint of heat-fusibility. % Or less is still more preferable, and 0 mol% is more preferable.

[Diol / diamine]
As the diol, an aliphatic diol is preferable and a linear aliphatic diol is more preferable from the viewpoint of excellent heat-fusibility of the produced adhesive.

  From the viewpoints of heat-fusibility and durability of the resulting adhesive, the diol has preferably 2 or more carbon atoms, more preferably 4 or more, still more preferably 8 or more, and still more preferably 10 or more. From the viewpoints of heat-fusibility and durability of the adhesive to be used, it is preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less.

  Specific examples of preferred aliphatic diols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1 , 5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1 , 14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentane Diol, 2,3-hexanediol, 3,4-hexanedi All, 2,4-hexanediol, 2,5-hexanediol, etc., from the viewpoint of heat-fusibility and durability, 1,6-hexanediol, 1,8-octanediol, 1, Group consisting of 9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol and 1,18-octadecanediol More preferably, at least one selected from the group consisting of 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol is more preferable. 1,10-decanediol and / or 1,12-dodecanediol are more preferable. As the diol, only one component may be used, or a plurality of components may be used in combination.

  The content of the aliphatic diol in the diol component is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol%, from the viewpoint of heat-fusibility and durability of the produced adhesive. More preferably, it is 90 mol% or more, still more preferably 95 mol% or more, still more preferably 99 mol% or more, and still more preferably substantially 100 mol%.

  Examples of diols other than aliphatic diols that can be used as diols include hydroxymethylfurfuryl alcohol; aromatic alcohols such as flange alcohol such as dihydroxyfuran. The amount of the aromatic alcohol is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and more preferably 0 mol% in the diol, from the viewpoint of heat-fusibility of the obtained adhesive. Even more preferred.

  In addition to the diol, a trihydric or higher polyhydric alcohol other than the diol may be used in combination. Examples of such alcohol include glycerin, pentaerythritol, trimethylolpropane and the like. The amount of the trihydric or higher polyhydric alcohol that can be used in combination is preferably 20 mol% or less with respect to 100 mol% of the total diol, from the viewpoint of the heat-fusibility and durability of the produced adhesive, 15 mol% or less is more preferable, 10 mol% or less is more preferable, 5 mol% or less is still more preferable, and 0 mol% is more preferable.

  As the diamine, an aliphatic diamine is preferable and a linear aliphatic diamine is more preferable from the viewpoints of heat-fusibility and durability of the produced adhesive.

  From the viewpoints of heat-fusibility and durability of the resulting adhesive, the diamine has preferably 2 or more carbon atoms, more preferably 4 or more, still more preferably 8 or more, and still more preferably 10 or more. From the viewpoints of heat-fusibility and durability of the adhesive, it is preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less.

  Preferred aliphatic diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,2-pentanediamine, 1,3-pentanediamine, 1,4-pentanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1 , 13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, and 1,6-hexanediamine, 1 from the viewpoint of heat-fusibility and durability , 8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine One or more selected from the group is preferred More preferably, at least one selected from the group consisting of 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine is more preferable, and 1,10-decanediamine and / or 1,12- More preferred is dodecanediamine. As the diamine, only one component may be used, or a plurality of components may be used in combination.

  The content of the aliphatic diamine is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol%, in the diamine component, from the viewpoint of heat-fusibility and durability of the produced adhesive. More preferably, it is 90 mol% or more, still more preferably 95 mol% or more, still more preferably 99 mol% or more, and still more preferably substantially 100 mol%.

  Examples of diamines other than aliphatic diamines that can be used as diamines include paraphenylenediamine, paraxylylenediamine, 2,4-toluenediamine, 4,4-diaminodiphenyl ether, and 2,2-bis [4- [4. -Aminophenoxy] phenyl] propane, bis [4- [4-aminophenoxy] phenyl] sulfone, 1,3-bis [4-aminophenoxy] benzene, aromatic diamines such as 4,4-diaminodiphenylsulfone, etc. It is done.

  In the present invention, in addition to the acid component, diol, and diamine, a hydroxycarboxylic acid compound may be used as a raw material for the resin as long as the present invention is not impaired. Examples of the hydroxycarboxylic acid compound include those containing at least one hydroxy group and one or more carboxyl groups in the molecule. The number of carbon atoms of the hydroxycarboxylic acid compound is preferably 3 or more, and more preferably 6 or less. Specifically, lactic acid (carbon number: 3, carboxyl group: 1, hydroxy group: 1), malic acid (carbon number: 4, carboxyl group: 2, hydroxy group: 1), tartaric acid (carbon number: 4, carboxyl) Group: 2, hydroxy group: 2), citric acid (carbon number: 6, carboxyl group: 3, hydroxy group: 1), isocitric acid (carbon number: 6, carboxyl group: 3, hydroxy group: 1), gluconic acid (Carbon number: 6, carboxyl group: 1, hydroxy group: 5) and the like.

  From the viewpoint of durability, the hydroxycarboxylic acid compound is preferably 100 mol% or less, more preferably 50 mol% or less, still more preferably 20 mol% or less, more preferably 10 mol with respect to 100 mol% of the dicarboxylic acid component. % Or less, more preferably 0 mol%.

  Only one of diol and diamine may be used, or both may be used together. When using a diol and a diamine together, the diamine is preferably used in an amount of 0.01 mol or more, more preferably 0.05 mol or more, preferably 100 mol or less, more preferably 20 mol or less with respect to 1 mol of the diol. .

  Among the resins obtained by condensing the acid component containing the dicarboxylic acid compound having a furan ring and diol and / or diamine, resins containing the following structural units are preferable from the viewpoint of durability and flexibility.

(In the formula, A represents a divalent aliphatic hydrocarbon group which may be substituted.)

  By using furan-2,5-dicarboxylic acid as the dicarboxylic acid compound having a furan ring, a resin containing the structural unit represented by the general formula (1) or (2) can be obtained. Therefore, furan-2,5-dicarboxylic acid is a more preferred compound as the dicarboxylic acid compound having a furan ring from the viewpoint of heat-fusibility and durability.

  A is preferably 2 or more carbon atoms, more preferably 4 or more, still more preferably 8 or more, and still more preferably 10 or more, from the viewpoints of heat-fusibility and durability of the produced adhesive. The divalent aliphatic hydrocarbon group which may have a substituent, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, from the viewpoint of heat-fusibility and durability of the adhesive. More preferably an alkylene group, still more preferably a linear alkylene group. Examples of the substituent include a carboxyl group.

  In order to satisfy the formula represented by the general formula (1), the above-mentioned diol may be used. From the viewpoint of heat-fusibility and durability, 1,6-hexanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol and 1, One or more selected from the group consisting of 18-octadecanediol is more preferable, and one or more selected from the group consisting of 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol is more preferable. 1,10-decanediol and / or 1,12-dodecanediol are more preferable.

  In order to satisfy the formula represented by the general formula (2), the above-mentioned diamine may be used. From the viewpoint of heat-fusibility and durability, 1,6-hexanediamine, 1,8-octane Selected from the group consisting of diamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,13-tridecyldiamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine. One or more selected from the group consisting of 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine, more preferably 1,10-decanediamine and / or 1,12-dodecanediamine is more preferred.

  The structural unit represented by the general formula (1) or (2) is present in the resin by introducing it as a copolymerization component or as a main polymerization component in the resin production process as described above. Can do.

[Production method of resin]
As a method for producing the resin in the present invention, known methods relating to the production of thermoplastic resins such as polyester, polycarbonate, polyamide and the like can be employed. Moreover, the polymerization reaction in this case can set the appropriate conditions employ | adopted conventionally, and is not restrict | limited in particular.

  Preferably, the dicarboxylic acid component and the diol and / or diamine are heated by heating the mixture containing the above-mentioned dicarboxylic acid component and diol and / or diamine as essential components and, if necessary, other components such as a catalyst and a plasticizer. Alternatively, it is prepared by causing a condensation reaction with diamine. The reaction is carried out until the number average molecular weight of the obtained resin falls within a preferable range described later.

  In the condensation reaction, the total amount of the diol and the diamine is preferably 1 mol or more, more preferably 1.2 mol with respect to 1 mol of the dicarboxylic acid component, from the viewpoint of enhancing the reactivity and improving the durability. More preferably, it is 1.5 mol or more, preferably 10 mol or less, more preferably 8 mol or less, and further preferably 5 mol or less.

  The heating temperature during the condensation reaction is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 270 ° C. or lower, more preferably 250 ° C. or lower. is there. The setting of the heating temperature is not particularly limited, and for example, it may be set to maintain a substantially constant temperature from the start to the end of the condensation reaction, or the temperature is increased when the condensation reaction has progressed to some extent. It may be a simple setting.

  The time required for the condensation reaction is, for example, preferably 1 hour or longer, more preferably 4 hours or longer, more preferably 6 hours or longer, preferably 15 hours or shorter, more preferably 10 hours or shorter.

The pressure in the reaction vessel during the condensation reaction may be normal pressure, but it is preferable to perform the condensation reaction under reduced pressure. The final degree of vacuum in the reaction vessel is, for example, preferably 1.33 × 10 ³ Pa or less, and more preferably 0.27 × 10 ³ Pa or less.

  It is preferable to proceed the reaction while appropriately removing gas components generated during the condensation reaction. For that purpose, the aspect which collect | recovers the fractions produced | generated with a condensation reaction using the reaction container provided with the cooling pipe, for example is preferable.

  When the catalyst is used in the condensation reaction, the catalyst addition time is not particularly limited as long as it is before the start of the pressure reduction reaction, and it may be added at the time of starting the raw material, or may be added at the start of the pressure reduction.

  In the production of the resin, chain extenders such as diisocyanate, diphenyl carbonate, dioxazoline, and silicate ester may be used.In particular, when a carbonate compound such as diphenyl carbonate is used, these carbonate compounds are added to the entire resin. It is also preferable to obtain polyester carbonate by adding 20 mol% or less, preferably 10 mol% or less, relative to 100 mol% of the constituent components.

  Moreover, in this invention, you may seal the polyester terminal group of resin with carbodiimide, an epoxy compound, monofunctional alcohol, or carboxylic acid.

  In this case, examples of the carbodiimide compound of the end-capping agent include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, the monocarbodiimide compound includes dicyclohexylcarbodiimide, diisopropyl. Carbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide, etc. Illustrated. These may be used individually by 1 type, and may mix and use 2 or more types.

  When the resin in the present invention is prepared by a condensation reaction, a catalyst may or may not be used depending on the type and combination of raw materials used. Examples of the catalyst include esterification catalysts such as tin compounds and titanium compounds. As the catalyst, only one component may be used, or a plurality of components may be used in combination.

  As the tin compound, a tin (II) compound having a Sn-O bond is more preferable from the viewpoint of polycondensation.

Examples of tin (II) compounds having a Sn-O bond include tin oxalate (II), tin (II) acetate, tin (II) octoate, octylic acid (2-ethylhexanoate) tin (II), and lauric acid. Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II), tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as stearoxytin (II) and oleyloxytin (II); tin oxide (II); tin (II) sulfate, etc., Sn-X (X is halogen) Examples of the tin (II) compound having a bond (showing an atom) include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, from the viewpoint of durability _{^{, (R 2 COO) 2 Sn}} ( wherein R ² represents an alkyl or alkenyl group having 5 to 19 carbon atoms) fatty acid and tin represented by ^{(II), (R 3 O} ) 2 Sn ( wherein R ³ Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by an alkyl group or alkenyl group having 6 to 20 carbon atoms), fatty acid tin represented by (R _² COO) ² Sn (II) and tin (II) oxide are more preferable, and tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferable.

Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ Among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolaminate are preferable, and these are, for example, Matsumoto Trading Co., Ltd. Also available as a commercial product.

  The amount of the catalyst present is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, and still more preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the diol and diamine and the dicarboxylic acid component. It is above, Preferably it is 2.0 mass parts or less, More preferably, it is 1.5 mass parts or less, More preferably, it is 1.0 mass part or less, More preferably, it is 0.1 mass part or less. Here, the amount of the catalyst present means the total amount of the catalyst subjected to the condensation polymerization reaction.

[Physical properties of resin]
The number average molecular weight of the resin used in the present invention is preferably 5000 or more, more preferably 8000 or more, still more preferably 10,000 or more, and still more preferably, from the viewpoints of heat fusion property and durability of the produced adhesive. From the viewpoint of resin productivity, it is preferably 150,000 or less, more preferably 100,000 or less, further preferably 80,000 or less, more preferably 60,000 or less, and even more preferably 50,000 or less. It is.

  The glass transition point (Tg) of the resin used in the present invention is preferably −50 ° C. or higher, more preferably −30 ° C. or higher, from the viewpoint of manufacturing the resin to be manufactured. From the viewpoint of improving the fusibility and durability, it is preferably 40 ° C. or lower, more preferably 20 ° C. or lower, further preferably 10 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −5 ° C. or lower.

  The melting point (Tm) of the resin used in the present invention is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C., from the viewpoint of improving the heat-fusability and durability of the produced adhesive. From the viewpoint of improving the heat-fusability and durability of the produced adhesive, it is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, further preferably 150 ° C. or lower, more preferably 120 ° C. or lower. is there.

The melt flow rate of the resin used in the present invention is preferably 0.1 g / min or more, more preferably 1 g / min or more, and still more preferably 5 g / min or more, from the viewpoint of the heat-fusibility of the produced adhesive. More preferably, it is 10 g / min or more, more preferably 15 g / min or more, further preferably 18 g / min or more, preferably 80 g / min or less, more preferably 60 g / min or less, and further preferably 50 g / min or less. is there.
The number average molecular weight, melting point, glass transition point, and melt flow rate of the resin used in the present invention can be determined by the methods described in the examples described later.

[Adhesive resin]
Said resin is one of the components which comprise an adhesive agent. Therefore, the above resin can be used as an adhesive resin, and the adhesive resin is one of the aspects of the present invention. The resin for adhesives of the present invention can be suitably applied to wood materials shown below.

〔adhesive〕
The adhesive of this invention contains said resin as an essential component, and contains a plasticizer or another component as needed. Since the adhesive of the present invention is excellent in heat-fusibility and durability, it can be preferably applied to wood materials. Preferred examples of the wood material include those described below.

  Preferred plasticizers are selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers and phosphate ester plasticizers from the viewpoint of heat-fusibility and durability. One or more selected from the above are preferred.

  Specific examples of the polyester plasticizer include succinic acid, glutaric acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid and the like, preferably a dicarboxylic acid having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, Propylene glycol (1,2-propanediol), 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol and the like preferably have 2 to 12 carbon atoms, More preferred examples include polyesters with 2 to 6 dialcohols. Further, it may be a compound in which a hydroxyl group or a carboxy group at a polyester terminal is esterified with a monocarboxylic acid or a monoalcohol and blocked.

  Specific examples of the polyhydric alcohol ester plasticizer include polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, and the above dialcohol or their (poly) oxyalkylene adducts, preferably 1 to 12 carbon atoms, more preferably May include mono-, di- or triesters with monocarboxylic acids having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

  As the polyvalent carboxylic acid ester plasticizer, a polyvalent carboxylic acid such as trimellitic acid and the above dicarboxylic acid, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to carbon atoms. And mono-, di- or triesters with 4 monoalcohols or their (poly) oxyalkylene adducts. Specifically, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate; tributyl trimellitic acid, trioctyl trimellitic acid, tri Trimellitic acid esters such as trihexyl melitrate; Adipic acid esters such as diisodecyl adipate and octyldecyl adipate; Citric acid esters such as triethyl acetyl citrate and tributyl acetyl citrate; Azelaic acid such as di-2-ethylhexyl azelate Esters; sebacic acid esters such as dibutyl sebacate and di-2-ethylhexyl sebacate; polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2 to 3 (hydroxyl group 1 The per ethylene oxide can be given 2-3 mols) esters of such.

  Examples of the phosphoric ester plasticizer include mono-, di- or triesters of phosphoric acid and the above monoalcohol or its (poly) oxyalkylene adduct. Specific examples include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, tricresyl phosphate, tris (ethoxyethoxyethyl) phosphate, and the like. it can.

  As the plasticizer, an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms) from the viewpoint of improving the heat fusion property and durability of the produced adhesive. And a polyester plasticizer having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms), a (poly) oxyalkylene group or 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms). ), A polyhydric alcohol ester plasticizer having an alkylene group, a (poly) oxyalkylene group or a polycarboxylic acid ester plasticizer having an alkylene group having 2 to 6 (preferably 2 to 4) carbon atoms, and (poly) And at least one selected from the group consisting of phosphate plasticizers having an oxyalkylene group or an alkylene group having 2 to 6 (preferably 2 to 4) carbon atoms. Preferred. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group. As the oxyalkylene group, an oxyethylene group, an oxypropylene group or an oxybutylene group is preferable, and an oxyethylene group or an oxypropylene group is more preferable.

  As the ester compound, one or more selected from the group consisting of the following ester compound (A), ester compound (B) and ester compound (C) is preferable because the adhesive is excellent in heat-fusibility and durability. When two or more types are used in combination, the same compound group or different compound groups may be used.

Compound (A)
The compound (A) is an ester compound having two or more ester groups in the molecule, and at least one alcohol component constituting the ester compound is an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group. It is an ester compound that is an alcohol added with an average of 0.5 to 5 mol.

Compound (B)
Compound (B) refers to formula (I):
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 N represents a number from 1 to 12. All R ^{1 s} may be the same or different, all R ² may be the same or different, and all R ³ may be the same or different. It is an ester compound represented by

Compound (C)
Compound (C) means: Formula (II):

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms. X, y and z are each independently a positive number indicating the average number of moles added of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less. is there.

Compound (A)
The ester compound contained in the compound (A) is a polyhydric alcohol ester or polycarboxylic acid ether ester having two or more ester groups in the molecule, and at least one alcohol component constituting the ester compound Is an ester compound which is an alcohol obtained by adding an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group.

  Specific compounds include an ester of acetic acid and glycerin ethylene oxide average 3 to 6 mol adduct (addition of 1 to 2 mol of ethylene oxide per hydroxyl group), an average addition mol number of acetic acid and ethylene oxide of 4 to 4 6 Esters with polyethylene glycol, Esters with polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2 to 3 (addition of 2 to 3 mol of ethylene oxide per hydroxyl group), Adipic acid and diethylene glycol monomethyl Esters with ethers and esters with 1,3,6-hexanetricarboxylic acid and diethylene glycol monomethyl ether are preferred.

Compound (B)
R ¹ in formula (I) represents an alkyl group having 1 to 4 carbon atoms, and two of them exist in one molecule and exist at both ends of the molecule. All R ¹ may be the same or different. R ¹ may be linear or branched as long as it has 1 to 4 carbon atoms. The number of carbon atoms of the alkyl group is preferably 1 to 4, and more preferably 1 to 2, from the viewpoint of improving heat-fusibility and durability. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, and iso-butyl group. Among them, heat fusion property and durability are improved. From the viewpoint of making it preferable, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

R ² in formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is a preferred example. Specific examples include an ethylene group, a 1,3-propylene group, and a 1,4-butylene group. From the viewpoint of improving heat-fusibility and durability, an ethylene group, a 1,3-propylene group, 1, A 4-butylene group is preferable and an ethylene group is more preferable. However, all R ² may be the same or different.

R ³ in formula (I) represents an alkylene group having 2 to 6 carbon atoms, and OR ³ is present in the repeating unit as an oxyalkylene group. R ³ may be linear or branched as long as it has 2 to 6 carbon atoms. As carbon number of an alkylene group, 2-6 are preferable from a viewpoint of improving heat-fusibility and durability, and 2-3 are more preferable. Specifically, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 2-methyl-1,3 -Propylene group, 1,2-pentylene group, 1,4-pentylene group, 1,5-pentylene group, 2,2-dimethyl-1,3-propylene group, 1,2-hexylene group, 1,5-hexylene Group, 1,6-hexylene group, 2,5-hexylene group, 3-methyl-1,5-pentylene group, among which ethylene group, 1,2-propylene group, 1,3-propylene group are preferable. However, all R ³ may be the same or different.

  m represents the average number of repeating oxyalkylene groups, and from the viewpoint of improving heat-fusibility and durability, the number of 1 to 6 is preferable, the number of 1 to 4 is more preferable, and the number of 1 to 3 is further preferable.

  n shows the average repeating number (average polymerization degree) of a repeating unit, and is a number of 1-12. From the viewpoint of improving heat-fusibility and durability, the number of 1 to 12 is preferable, the number of 1 to 6 is more preferable, and the number of 1 to 5 is more preferable. The average degree of polymerization may be determined by analysis such as NMR, but can be calculated according to the method described in Examples below.

Specific examples of the compound represented by formula (I) include: R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1,3-propylene group , M is a number of 1 to 4, and n is a number of 1 to 6, R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1, A compound which is a 3-propylene group and m is a number of 1 to 3 and n is a number of 1 to 5 is more preferable.

  Among such structures, from the viewpoint of improving durability, at least one dibasic acid selected from succinic acid, glutaric acid, and adipic acid, diethylene glycol, triethylene glycol, 1,2-propanediol, and 1, At least one dihydric alcohol oligoester selected from 3-propandiol (in formula (I), n = 1.2 to 3) is preferred.

  The compound represented by the formula (I) preferably has an acid value of 1.50 mgKOH / g or less, more preferably 1.00 mgKOH / g or less, from the viewpoint of improving heat-fusibility and durability. The value is preferably 10.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less, and still more preferably 3.0 mgKOH / g or less, from the viewpoint of improving heat-fusibility and durability. In addition, in this specification, the acid value and hydroxyl value of a plasticizer can be measured according to the method as described in the below-mentioned Example.

  In addition, the number average molecular weight of the compound represented by the formula (I) is preferably 300 to 1500, more preferably 300 to 1000, from the viewpoint of improving heat-fusibility and durability. In the present specification, the number average molecular weight of the plasticizer can be calculated according to the method described in Examples described later.

  The compound represented by the formula (I) has an alkyl esterification rate (terminal alkyl esterification rate) with respect to two molecular ends, preferably 95% or more, from the viewpoint of improving heat-fusibility and durability. Preferably it is 98% or more. In the present specification, the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in Examples described later.

Compound (C)
The compound represented by the formula (II) is a polyether-type phosphate triester, which may be a symmetric structure or an asymmetric structure. However, from the viewpoint of ease of production, a phosphate triester having a symmetric structure is preferable.

R ⁴ , R ⁵ , and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and an ethyl group, a propyl group, and a butyl group are preferable. Further, from the viewpoint of improving heat-fusibility and durability, an alkyl group having 2 to 3 carbon atoms, that is, an ethyl group and a propyl group are more preferable.

A ¹ , A ² , and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms, and may be linear or branched. Specific examples include an ethylene group, an n-propylene group, and an isopropylene group. Among these, an ethylene group is preferable from the viewpoint of improving heat-fusibility and durability. A ¹ , A ² and A ³ form an oxyalkylene group (alkylene oxide) with an adjacent oxygen atom to form a repeating structure in the compound represented by the formula (II).

  x, y, and z are each independently a positive number indicating the average added mole number of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less. Among these, from the viewpoint of improving heat-fusibility and durability, x, y, and z are positive numbers, and x + y + z is preferably more than 3 and less than 12, more than 4 and more than 12 The number satisfying less than is more preferable, and the number satisfying 6 or more and 9 or less is more preferable.

Specific examples of the compound represented by the formula (II) include tris (ethoxyethoxyethyl) phosphate [in the formula (II), R ⁴ , R ⁵ and R ⁶ are all ethyl groups, A ¹ , A ² , A ³ is an ethylene group, x, y and z are all 2; in addition to x + y + z = 6], tris (methoxyethoxyethyl) phosphate (x + y + z = 6), tris (propoxyethoxyethyl) phosphate (x + y + z = 6) ), Tris (butoxyethoxyethyl) phosphate (x + y + z = 6), tris (methoxyethoxyethoxyethyl) phosphate (x + y + z = 9), tris (ethoxyethoxyethoxyethyl) phosphate (x + y + z = 9), tris (propoxyethoxyethoxyethyl) Symmetric polyether-type phosphate triesters such as phosphate (x + y + z = 9) Bis (ethoxyethoxyethyl) methoxyethoxyethoxyethyl phosphate (x + y + z = 7), bis (methoxyethoxyethoxyethyl) ethoxyethoxyethyl phosphate (x + y + z = 8), bis (ethoxyethoxyethyl) {butoxyethoxyethyl} phosphate (x + y + z = 6) or the like, or a mixture of a polyoxyethylene adduct or a polyoxypropylene adduct of an alcohol having 1 to 4 carbon atoms with phosphoric acid triester to satisfy the formula (II). Asymmetric polyether-type phosphates are mentioned. From the viewpoint of improving heat-fusibility and durability, tris (ethoxyethoxyethyl) phosphate, tris (propoxyethoxyethyl) phosphate, tris (ethoxyethoxyether) Kishiechiru) phosphate, tris (propoxyethoxy ethoxyethyl) phosphate is preferred, tris (ethoxyethoxyethyl) phosphate is more preferable.

  The content of one or more kinds selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer in the plasticizer, Or the content of the ester compound which has a (poly) oxyalkylene group or a C2-C6 alkylene group, More preferably, the polyester plasticizer which has a (poly) oxyalkylene group or a C2-C6 alkylene group , One or more contents selected from the group consisting of a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer, more preferably the compound group (A) to As the content of one or more compounds selected from the group consisting of (C), is the viewpoint of improving the heat-fusibility and durability of the adhesive? , Preferably 50 wt% or more, more preferably 80 wt% or more, more preferably 90 mass% or more, further preferably substantially 100 mass%. In the present specification, the content of the plasticizer means the total content when a plurality of compounds are contained.

  The amount of the plasticizer in the adhesive of the present invention is preferably 20 parts by mass or more, preferably 100 parts by mass of the resin, from the viewpoint of improving the heat fusion property and durability of the produced adhesive. 30 parts by mass or more, more preferably 50 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and further preferably 150 parts by mass, from the viewpoint of suppressing a decrease in durability of the produced adhesive. It is at most 120 parts by mass, more preferably at most 120 parts by mass, even more preferably at most 100 parts by mass, even more preferably at most 80 parts by mass.

  The content of the resin in the adhesive of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more from the viewpoint of adhesiveness, and a plasticizer is contained. From the viewpoint of improving heat-fusibility and durability, it is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. The plasticizer content is heat-fusible. From the viewpoint of improving durability, it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and from the viewpoint of adhesiveness, preferably 70% by mass or less, more preferably It is 60 mass% or less, More preferably, it is 50 mass% or less.

  The adhesive of the present invention can contain other components other than those described above as long as the effects of the present invention are not hindered. For example, an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, Inorganic fillers, fungicides, antibacterial agents, foaming agents, flame retardants and the like can be included.

  These other components may be added to the reaction apparatus before the polymerization reaction, or may be added to the conveying apparatus or the like from the start of the polymerization reaction to the end of the polymerization reaction. It may be added before extraction. Moreover, you may add to the product after extraction.

[Adhesion method]
In the bonding method of the present invention, the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component obtained by condensing a dicarboxylic acid component containing the dicarboxylic acid compound having a furan ring and a diol and / or diamine is obtained. This is an adhesion method in which a resin having a melting point of 50 ° C. or higher and 200 ° C. or lower is used.

  When bonding, it is preferable to raise the temperature of the resin above the melting point of the resin. From the viewpoint of adhesiveness, it is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 100 ° C. or higher, and still more preferably 130 ° C. or higher. From the viewpoint of suppressing the decomposition of the resin, preferably 240 ° C. It is preferable that the bonding be performed at a temperature of not higher than ° C, more preferably not higher than 220 ° C, still more preferably not higher than 200 ° C, still more preferably not higher than 190 ° C.

  Examples of the object to be bonded include a pulverized product of a wooden material, a non-woven fabric, a woven fabric, a resin film, and a knitted material, which will be described later, and a pulverized product of a wooden material is preferable.

[Pet waste treatment agent]
The excrement disposal material for pet of the present invention can be produced by adhering the pulverized material of the wood material using the adhesive of the present invention. Specifically, the excrement disposal material for pet of the present invention is produced by extruding the adhesive of the present invention and the pulverized material of the wood material at a temperature equal to or higher than the melting point of the resin in the adhesive. Can do.

  Either wood or grass can be used as the material of the wood material. Examples of the woody material include a pulverized product of wood (a pulverized product of wood or bark), a residue of seed oil, a pulverized husk of grain, and a pulverized herbaceous material. From the viewpoint of moldability, heat-fusibility, and durability, it is preferable to use a pulverized product of wood, particularly a crushed product of coniferous trees such as cedar, pine or cypress. The size of the pulverized product is preferably 0.01 mm or more, more preferably 0.02 mm or more, further preferably 0.05 mm or more from the viewpoint of use in excrement treatment, and from the viewpoint of moldability, preferably 1 cm or less. More preferably, it is 5 mm or less, More preferably, it is 2 mm or less. The particle diameter is determined by measuring the maximum diameter of particles and averaging the number of 50 particles.

  The excrement disposal material for pets is a pulverized product of plant-derived material, which is the above wood material, preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and further preferably 85% by mass. %, Preferably 99% by mass or less, more preferably 95% by mass or less, and preferably contains 1% by mass or more, more preferably 5% by mass or more, preferably 30% by mass. Hereinafter, more preferably 25% by mass or less, further preferably 20% by mass or less, and further preferably 15% by mass or less.

  The excrement disposal material for pets is preferably formed into a predetermined shape, preferably a cylindrical shape. The diameter of the molded product is preferably 1 mm or more, more preferably 2 mm or more, further preferably 3 mm or more, further preferably 4 mm or more, preferably 7 mm or less, more preferably 6 mm or less, and further preferably 5 mm or less. . The length of the molded product is preferably 3 mm or more, more preferably 5 mm or more, further preferably 6 mm or more, further preferably 7 mm or more, preferably 30 mm or less, more preferably 25 mm or less, still more preferably 20 mm or less, More preferably, it is 15 mm or less. When there is a major axis and a minor axis, the major axis is measured. The length measures the maximum length of the column part. These are obtained by averaging 50 pieces each.

  The pet excretion treating agent is formed into a pellet by press-molding the pulverized material of the adhesive and the wood material using, for example, a compression extrusion molding machine. The compression extrusion molding machine is provided with a mold in which an extrusion hole is formed and a pressing roll for pressing a mixture of an adhesive and a pulverized product into the extrusion hole, and the pressing roll is disposed adjacent to the mold. It is preferable to use a high pressure extrusion molding machine. An example of such a high pressure extrusion molding machine is a sprout molding machine. When a high-pressure extrusion molding machine such as a sprout molding machine is used, the mixture can be pushed into the molding hole at a high pressure. Further, since the extrusion hole is deep, the resistance force generated on the inner wall of the extrusion hole can be increased. Furthermore, since compaction is achieved as the diameter of the extrusion hole is smaller, a compression molded product having better compressibility can be obtained as the pellet has a smaller diameter. Therefore, the mixture can be consolidated by a high extrusion resistance, and a compression molded product (pellet) excellent in shape retention before use can be obtained.

  In molding by the molding machine, it is preferable to raise the temperature of the mixture above the melting point of the resin. From the viewpoint of moldability, it is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 100 ° C. or higher, still more preferably 130 ° C. or higher, and from the viewpoint of suppressing decomposition of the resin, preferably 240 ° C. It is preferable to mold at a temperature of not higher than ° C, more preferably not higher than 220 ° C, still more preferably not higher than 200 ° C, still more preferably not higher than 190 ° C. Natural heat generation due to compression and friction of the mixture inside the extruder may be used, or a heating element such as an electric heater may be used. By melting and solidifying the resin, a pulverized product of plant-derived material is adhered by the adhesive, and a predetermined molded product is obtained.

  The excrement disposal material of the present invention can be spread as it is on a shallow tray or the like and used as so-called cat sand.

  The excrement disposal material of the present invention may contain an antibacterial agent, a coloring agent, and the like as necessary in addition to the above-described components. The amount of these components is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the excrement disposal material. Antibacterial agents include sodium benzoate, sorbic acid, potassium sorbate, didecylmethylammonium chloride, benzalkonium chloride, polyphenols, silver, copper and the like.

  The present invention further discloses the following items, manufacturing methods, and uses with respect to the above-described embodiments.

[1] An adhesive containing a resin,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. An adhesive which is a resin exceeding mol%, and the melting point of the resin is 50 ° C. or higher and 200 ° C. or lower.

[2] The amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is preferably 93 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and even more preferably 99 mol% or more. The adhesive according to [1], which is more preferably substantially 100%.
[3] The group in which the dicarboxylic acid compound having a furan ring is composed of furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid and furan-3,4-dicarboxylic acid. The adhesive according to [1] or [2], wherein the adhesive is one or more selected from flanged carboxylic acid compounds.
[4] The dicarboxylic acid component preferably further contains an aliphatic dicarboxylic acid compound having 2 or more carbon atoms, more preferably 6 or more carbon atoms, preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms. ] ~ [3] Any one adhesive.
[5] The aliphatic dicarboxylic acid compound is preferably oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, acids of these acids [4] The adhesive according to [4], which is one or more aliphatic dicarboxylic acid compounds selected from the group consisting of anhydrides and alkyl esters of 1 to 3 carbon atoms of these acids.
[6] The amount of the aliphatic dicarboxylic acid compound in the dicarboxylic acid component is preferably less than 10 mol%, more preferably 7 mol% or less, still more preferably 5 mol% or less, even more preferably 2 mol% or less, The adhesive according to [4] or [5], more preferably 1 mol% or less, and still more preferably 0 mol%.

[7] The diol has preferably 2 or more carbon atoms, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, preferably 18 or less, more preferably 14 or less, still more preferably 12 The adhesive according to any one of [1] to [6] above.
[8] The adhesive according to any one of [1] to [7], wherein the diol is preferably an aliphatic diol, more preferably a linear aliphatic diol.
[9] Diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentanediol, 2,3- Hexanediol, 3,4-hexanediol, 2,4-hexanediol and 2,5- One or more aliphatic diols selected from the group consisting of xylene diols are preferred, such as 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 -More preferably one or more selected from the group consisting of dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol and 1,18-octadecanediol, One or more selected from the group consisting of octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol is more preferred, and 1,10-decanediol and / or 1,12- The adhesive according to any one of [1] to [8], wherein dodecanediol is still more preferable.

[10] The content of the aliphatic diol in the diol component is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and even more preferably. Is at least 95 mol%, more preferably at least 99 mol%, and even more preferably at most 100 mol%, [1] to [9].
[11] The carbon number of the diamine is preferably 2 or more, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, preferably 18 or less, more preferably 14 or less, and still more preferably 12 The adhesive according to any one of [1] to [10] above.

[12] The adhesive according to any one of [1] to [11], wherein the diamine is preferably an aliphatic diamine, more preferably a linear aliphatic diamine.
[13] diamine is ethylenediamine, 1,2-propanediamine 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,2-pentanediamine, 1 , 3-pentanediamine, 1,4-pentanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1, One or more selected from the group consisting of 13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, and 1,18-octadecanediamine are preferable, 1,6-hexanediamine, 1,8 -From the group consisting of octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine More preferably one or more selected One or more selected from the group consisting of 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine is more preferable, and 1,10-decanediamine and / or 1,12-dodecanediamine is more preferable. The adhesive according to any one of [1] to [12], which is more preferable.
[14] The content of the aliphatic diamine in the diamine component is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and even more preferably. Is at least 95 mol%, more preferably at least 99 mol%, and even more preferably substantially at 100 mol%, [1] to [13].

[15] As a resin raw material, one or more hydroxycarboxylic acid compounds are preferably 100 mol% or less, more preferably 50 mol% or less, still more preferably 20 mol% or less, based on 100 mol% of the dicarboxylic acid component. The adhesive according to any one of [1] to [14], more preferably 10 mol% or less, and still more preferably 0 mol%.
[16] The resin is represented by the following general formula (1) or (2):

(Wherein A represents a divalent aliphatic hydrocarbon group which may be substituted.) The adhesive according to any one of [1] to [15], which is a resin including a structural unit represented by: .
[17] A is preferably 2 or more, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less. The adhesive according to [16], wherein a divalent aliphatic hydrocarbon group which may have a substituent is preferable, an alkylene group is more preferable, and a linear alkylene group is further preferable.
[18] The resin is produced by heating a mixture containing a dicarboxylic acid component and a diol and / or diamine to cause a condensation reaction between the dicarboxylic acid component and the diol and / or diamine, [1] to [17] Any one adhesive.
[19] The total amount of diol and diamine is preferably 1 mol or more, more preferably 1.2 mol or more, still more preferably 1.5 mol or more, preferably 10 mol with respect to 1 mol of the dicarboxylic acid component. Hereinafter, the adhesive according to any one of [1] to [18], more preferably 8 mol or less, and further preferably 5 mol or less.
[20] The heating temperature during the condensation reaction is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 270 ° C. or lower, more preferably 250 The adhesive according to any one of the above [1] to [19], which is not higher than ° C.

[21] A condensation reaction is carried out using one or more esterification catalysts selected from the group consisting of tin compounds and titanium compounds, and the amount of the catalyst is 100 parts by mass of the total amount of diol, diamine and dicarboxylic acid component Is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, further preferably 0.01 parts by mass or more, preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass. [1] to [20] The adhesive according to any one of [1] to [20], which is not more than part by mass, more preferably not more than 1.0 part by mass, and more preferably not more than 0.1 part by mass.
[22] The number average molecular weight of the resin is preferably 5000 or more, more preferably 8000 or more, further preferably 10,000 or more, further preferably 15,000 or more, preferably 150,000 or less, more preferably 100,000. Hereinafter, the adhesive according to any one of [1] to [21], more preferably 80,000 or less, further preferably 60,000 or less, and further preferably 50,000 or less.
[23] The glass transition point of the resin is preferably −50 ° C. or higher, more preferably −30 ° C. or higher, preferably 40 ° C. or lower, more preferably 20 ° C. or lower, still more preferably 10 ° C. or lower, still more preferably. The adhesive according to any one of [1] to [22], which is 0 ° C. or lower, more preferably −5 ° C. or lower.
[24] The melting point of the resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, more preferably 150 ° C. or lower, More preferably, the adhesive according to any one of [1] to [23], which is 120 ° C. or lower.

[25] The melt flow rate of the resin is preferably 0.1 g / min or more, more preferably 1 g / min or more, further preferably 5 g / min or more, further preferably 10 g / min or more, and further preferably 15 g / min or more. More preferably, it is 18 g / min or more, preferably 80 g / min or less, more preferably 60 g / min or less, and still more preferably 50 g / min or less. Any one of [1] to [24] above Agent.
[26] The adhesive according to any one of [1] to [25], wherein the adhesive further contains a plasticizer.
[27] The plasticizer content in the adhesive is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass. [26] The adhesive according to [26], which is not more than mass%, more preferably not more than 50 mass%.
[28] The amount of the plasticizer in the adhesive is preferably 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, preferably 200 parts by mass with respect to 100 parts by mass of the resin. Or less, more preferably 180 parts by mass or less, more preferably 150 parts by mass or less, further preferably 120 parts by mass or less, further preferably 100 parts by mass or less, and further preferably 80 parts by mass or less. 27] Adhesive.

[29] The plasticizer is preferably one or more selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer, [26 ]-[28] Any one adhesive.
[30] An ester compound in which the plasticizer has a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms) is preferred, and a (poly) oxyalkylene group or 2 to 6 carbon atoms (preferably). Is a polyester plasticizer having an alkylene group of 2-4), a polyhydric alcohol ester plasticizer having a (poly) oxyalkylene group or an alkylene group of 2-6 carbon atoms (preferably 2-4), (poly) Polycarboxylic acid ester plasticizer having an oxyalkylene group or an alkylene group having 2 to 6 (preferably 2 to 4) carbon atoms, and a (poly) oxyalkylene group or 2 to 6 (preferably 2 to 4) carbon atoms The adhesive according to any one of [26] to [29], wherein at least one selected from the group consisting of a phosphate ester plasticizer having an alkylene group is more preferable.

[31] The ester compound as a plasticizer is preferably one or more selected from the group consisting of the following ester compound (A), the following ester compound (B) and the following ester compound (C), [26] to [30] Any one adhesive.
Compound (A): An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 2 to 3 alkylene oxides per hydroxyl group .Ester compound compound (B) which is alcohol added in 5 to 5 mol: Formula (I)
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 N represents a number from 1 to 12. All R ^{1 s} may be the same or different, all R ² may be the same or different, and all R ³ may be the same or different. Ester compound compound (C) represented by formula (II)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms. X, y and z are each independently a positive number indicating the average number of moles of oxyalkylene group added, and x + y + z is a number exceeding 3 and satisfying 12 or less.)
[32] The ester compound (A) is preferably a polyhydric alcohol ester or polyhydric carboxylic acid ether ester having two or more ester groups in the molecule, and at least one alcohol component constituting the ester compound Is an ester compound which is an alcohol obtained by adding an average of 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group, and more preferably an average of 3 to 6 moles of an adduct of acetic acid and glycerol (hydroxyl group) 1 to 2 mol addition of ethylene oxide per one), an ester of acetic acid and ethylene glycol having an average addition mol number of 4 to 6, and an average addition mol number of succinic acid and ethylene oxide of 2 to 3 Polyethylene glycol monomethyl ether (ethylene oxide per hydroxyl group) 1 type of ester selected from the group consisting of an ester with 2 to 3 mol addition of aldehyde), an ester with adipic acid and diethylene glycol monomethyl ether, and an ester with 1,3,6-hexanetricarboxylic acid and diethylene glycol monomethyl ether The adhesive according to any one of [26] to [31] above.

[33] The ester compound (B) is preferably such that R ¹ in the formula (I) is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1,3-propylene group Wherein m is a number of 1 to 4 and n is a number of 1 to 6, more preferably, R ¹ in formula (I) is all methyl group, R ² is ethylene group or 1,4-butylene Any one of the above [26] to [32], wherein R ³ is an ethylene group or a 1,3-propylene group, m is a number of 1 to 3, and n is a number of 1 to 5. Glue.
[34] The ester compound (C) is preferably such that R ⁴ , R ⁵ and R ^{6 in} formula (II) are each independently selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. One or more selected from the group consisting of A ¹ , A ² and A ³ are each independently one or more selected from the group consisting of an ethylene group, an n-propylene group and an isopropylene group, Form an oxyalkylene group with an adjacent oxygen atom, x, y and z are each independently a positive number, and x + y + z exceeds 3, preferably exceeds 4, more preferably 6 or more The adhesive according to any one of [26] to [33], which is a number satisfying 12 or less, preferably less than 12, more preferably 9 or less.
[35] The ester compound (C) is tris (ethoxyethoxyethyl) phosphate, tris (methoxyethoxyethyl) phosphate, tris (propoxyethoxyethyl) phosphate, tris (butoxyethoxyethyl) phosphate, tris (methoxyethoxyethoxyethyl) phosphate , Tris (ethoxyethoxyethoxyethyl) phosphate, tris (propoxyethoxyethoxyethyl) phosphate, bis (ethoxyethoxyethyl) methoxyethoxyethoxyethyl phosphate, bis (methoxyethoxyethoxyethyl) ethoxyethoxyethyl phosphate, bis (ethoxyethoxyethyl) { Butoxyethoxyethyl} phosphate, and polyoxyethylene adduct or polyoxypro of alcohol having 1 to 4 carbon atoms Any one of the above [26] to [34], wherein the mixture of pyrene adducts is at least one selected from the group consisting of asymmetric polyether-type phosphate esters obtained by phosphoric esterification so as to satisfy formula (II) One adhesive.

[36] In the plasticizer, preferably one or more selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers and phosphate ester plasticizers Content, or content of an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, more preferably a polyester having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms One or more contents selected from the group consisting of a plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer, more preferably the compound group ( The content of one or more compounds selected from the group consisting of A) to (C) is preferably 50% by mass or more, more preferably 80 qualities. The adhesive according to any one of the above [26] to [35], which is contained in an amount of not less than%, more preferably not less than 90% by mass, and still more preferably substantially 100% by mass.
[37] The content of the resin in the adhesive is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass. % Or less, more preferably 70% by mass or less, the adhesive according to any one of [1] to [36].
[38] The amount of a dicarboxylic acid compound having a furan ring in the dicarboxylic acid component obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine exceeds 90 mol%. A resin that is preferably at least 93 mol%, more preferably at least 95 mol%, even more preferably at least 98 mol%, even more preferably at least 99 mol%, even more preferably substantially 100%, The melting point of the resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 150 ° C. or lower, more preferably 120 ° C. Resin for adhesive which is below ℃.

[39] The resin for adhesive according to [38], which can be suitably applied to a wood material.
[40] The adhesive according to any one of [1] to [37] and the pulverized wood material, preferably at a temperature equal to or higher than the melting point of the resin in the adhesive, and preferably 50 ° C or higher, More preferably, it is 70 ° C or higher, more preferably 100 ° C or higher, still more preferably 130 ° C or higher, preferably 240 ° C or lower, more preferably 220 ° C or lower, still more preferably 200 ° C or lower, still more preferably. A feces excrement treating material obtained by extrusion molding at 190 ° C. or lower.
[41] The woody material is preferably one or more selected from the group consisting of pulverized wood (wood or bark crushed), seed oil residue, grain hull crushed and herb crushed, More preferably, the excrement disposal material for pets according to the above [40], which is a pulverized product of one or more kinds of wood or bark selected from the group consisting of cedar family, pine family and cypress family.
[42] The size of the pulverized product is preferably 0.01 mm or more, more preferably 0.02 mm or more, further preferably 0.05 mm or more, preferably 1 cm or less, more preferably 5 mm or less, and even more preferably 2 mm or less. The excrement disposal material for pets according to [40] or [41].
[43] The content of the pulverized wood material is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, further preferably 85% by mass or more, and preferably 99% by mass. % Or less, and more preferably 95% by mass or less, the pet excrement disposal material according to any one of [40] to [42].

[44] The adhesive content is preferably 1% by mass or more, more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. More preferably, the excrement disposal material for pet according to any one of [40] to [43], which is 15% by mass or less.
[45] Preferably, the molded product is formed into a cylindrical shape, and the diameter of the molded product is preferably 1 mm or more, more preferably 2 mm or more, further preferably 3 mm or more, more preferably 4 mm or more, preferably 7 mm or less, more preferably 6 mm or less, more preferably 5 mm or less, and the length of the molded product is preferably 3 mm or more, more preferably 5 mm or more, further preferably 6 mm or more, more preferably 7 mm or more, The pet excrement disposal material according to any one of [40] to [44], which is preferably 30 mm or less, more preferably 25 mm or less, further preferably 20 mm or less, and further preferably 15 mm or less.

[46] Any of the above [40] to [45], which is produced by pressure molding the pulverized product of any one of the adhesives [1] to [37] with a compression extrusion molding machine One pet excrement disposal material.
[47] The amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine exceeds 90 mol%. A resin that is preferably at least 93 mol%, more preferably at least 95 mol%, even more preferably at least 98 mol%, even more preferably at least 99 mol%, even more preferably substantially 100%, The melting point of the resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 150 ° C. or lower, more preferably 120 ° C. An adhesion method in which a resin having a temperature of ℃ or less is used for adhesion.
[48] The bonding method according to [47], wherein a pulverized material, a nonwoven fabric, a woven fabric, a resin film, a knitted fabric or the like of a wooden material is bonded.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited at all by the Example. “Part” means part by mass.

Production Example 1
In a 2 L reaction vessel equipped with a stirring blade, a nitrogen inlet, and a cooling tube, 300 g (1.92 mol) of 2,5-furandicarboxylic acid, 520 g (5.77 mol) of 1,4-butanediol and 0.1 g of tin octylate were added. 3 g (0.00074 mol) was measured and charged. The mixture was heated to 180 ° C. while starting stirring and introducing nitrogen at 500 mL / min. While maintaining this temperature, the fraction produced by the condensation reaction was recovered over 3 hours. Next, the mixture was further heated to raise the temperature in the reaction vessel to 230 ° C., and the pressure was gradually reduced to 1 Pa, and the fraction was collected. After reaching 230 ° C., this temperature was maintained and polymerization was continued for 6 hours under reduced pressure (pressure 50 Pa) to obtain a resin in the reaction vessel.

Production Example 2
A resin was obtained in the same manner as in Production Example 1 except that 520 g of 1,4-butanediol in Production Example 1 was changed to 844 g (5.77 mol) of 1,8-octanediol.

Production Example 3
A resin was obtained in the same manner as in Production Example 1, except that 520 g of 1,4-butanediol in Production Example 1 was changed to 1006 g (5.77 mol) of 1,10-decanediol.

Production Example 4
A resin was obtained in the same manner as in Production Example 1 except that 520 g of 1,4-butanediol in Production Example 1 was changed to 1167 g (5.77 mol) of 1,12-dodecanediol.

Production Example 5
A resin was obtained in the same manner as in Production Example 1, except that 520 g of 1,4-butanediol in Production Example 1 was changed to 1156 g (5.77 mol) of 1,12-diaminododecane.

Production Example 6
520 g of 1,4-butanediol in Production Example 1 was changed to 546 g (6.06 mol), and 20.4 g (0.101 mol) of sebacic acid was added to the reaction vessel together with 2,5-furandicarboxylic acid and the like. Except that, the same operation as in Production Example 1 was performed to obtain a resin. The molar ratio of 2,5-furandicarboxylic acid to sebacic acid (2,5-furandicarboxylic acid / sebacic acid) was 95/5.

Production Example 7
520 g of 1,4-butanediol in Production Example 1 was changed to 611 g (6.78 mol), and 68.5 g (0.339 mol) of sebacic acid was added to the reaction vessel together with 2,5-furandicarboxylic acid and the like. Except that, the same operation as in Production Example 1 was performed to obtain a resin. The molar ratio of 2,5-furandicarboxylic acid to sebacic acid (2,5-furandicarboxylic acid / sebacic acid) was 85/15.

Measurement of molecular weight The molecular weight of the resin was measured under the following conditions.
Analytical instrument: manufactured by Tosoh Corporation, HLC-8320GPC
Detector: Differential refraction detector Eluent: Hexafluoroisopropanol solution whose concentration of sodium trifluoroacetate is 5 mM Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Molecular weight standard: A polymethyl methacrylate (PMMA) standard was used, and the number average molecular weight was determined to obtain the molecular weight of the resin.

Measurement of Melting Point and Glass Transition Temperature The melting point (Tm) and glass transition temperature (Tg) of the resin were measured under the following conditions.
Apparatus name: Differential scanning calorimetry apparatus manufactured by TA Instruments Pan: Platinum pan Sample mass: 10 mg
Temperature increase rate: 10 ° C / min

Measurement of Melt Flow Rate According to the method described in JIS K7210, the melt flow rate (MFR) of the resin was measured under the following conditions.
Temperature: 190 ° C
Load: 21.18N load

  Table 1 shows the physical property values of the resins obtained in Production Examples 1 to 7.

Plasticizer Production Example 1 (Diester of succinic acid and triethylene glycol monomethyl ether)
A 3 L flask equipped with a stirrer, thermometer and dehydration tube was charged with 500 g of succinic anhydride, 2463 g of triethylene glycol monomethyl ether, and 9.5 g of paratoluenesulfonic acid monohydrate, and nitrogen (500 mL / min) was added to the space. While blowing, the reaction was carried out at 110 ° C. for 15 hours under reduced pressure (4 to 10.7 kPa). The acid value of the obtained reaction liquid was 1.6 (KOHmg / g).

  After adding 27 g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) to the reaction liquid and stirring and filtering at 80 ° C. and 2.7 kPa for 45 minutes, the liquid temperature is 115 to 200 ° C. and the pressure is 0.03 kPa for 5 hours. The triethylene glycol monomethyl ether was distilled off. Subsequently, after cooling to 80 ° C., the residual liquid was filtered under reduced pressure to obtain a diester of succinic acid and triethylene glycol monomethyl ether as a filtrate. Let the obtained diester be the plasticizer 1.

Plasticizer production example 2 (oligoester with dimethyl succinate and diethylene glycol)
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 999 g (9.41 mol) of diethylene glycol and 23.6 g of a methanol solution containing 28 mass% sodium methoxide as a catalyst (sodium methoxide 0) .122 mol) was added, and methanol was distilled off while stirring at normal pressure (101.3 kPa) and 120 ° C. for 0.5 hour. Thereafter, 4125 g (28.2 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 2 hours to distill off methanol, and the pressure was returned to normal pressure. Further, 28 mass% sodium methoxide-containing methanol as a catalyst. 4.4 g of solution (0.023 mol of sodium methoxide) was added, and methanol was distilled at 100 ° C. by gradually lowering the pressure from normal pressure to 2.9 kPa over 2 hours.

  Then, after cooling to 80 ° C., 41 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was raised at a pressure of 0.3 kPa and the temperature from 70 ° C. to 190 ° C. over 4 hours, and the remaining dimethyl succinate was distilled off to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.51 mol with respect to 100 mol of dicarboxylic acid ester. The obtained liquid had an acid value of 0.48 mg KOH / g, a hydroxyl value of 1.1 mg KOH / g, a molecular weight of 450, and a terminal alkyl esterification rate of 99.4%. Let the obtained oligoester be the plasticizer 2.

Plasticizer Production Example 3 (Tris (ethoxyethoxyethyl) phosphate)
To a 1 liter four-necked flask, 600 g (4.47 mol) of diethylene glycol monoethyl ether was added and stirred under reduced pressure (20 kPa) while blowing dry nitrogen gas at a flow rate of 50 mL per minute. Next, 114 g (0.745 mol) of phosphorus oxychloride was slowly added dropwise while maintaining the reaction system at room temperature (15 ° C.), and then aged at 40 to 60 ° C. for 5 hours. Thereafter, 149 g of a 16% by mass aqueous sodium hydroxide solution was added for neutralization, and excess unreacted diethylene glycol monoethyl ether was distilled off under reduced pressure at a temperature of 70 to 120 ° C., and further contacted with steam to obtain crude phosphoric acid. 367 g of triester was obtained.

  Further, 300 g of a 16% by mass aqueous sodium chloride solution was added to the crude phosphoric acid triester for washing. Thereafter, the separated lower layer was removed, and the remaining upper layer was dehydrated under reduced pressure at 75 ° C., and the solid content was further removed by filtration to obtain 266 g of the desired tris (ethoxyethoxyethyl) phosphate (yield) 80%). The obtained phosphoric acid triester is designated as plasticizer 3.

[Acid value, hydroxyl value and saponification value of plasticizer]
Acid value: Analysis is performed according to the test method of JIS K 0070, except that toluene / ethanol = 2/1 (volume ratio) is used as a titration solvent.
Hydroxyl value: Analysis is performed according to the test method of JIS K 0070, except that acetic anhydride / pyridine = 1/4 (volume ratio) is used as the acetylating reagent and the addition amount is 3 mL.
Saponification value: Analysis is performed according to the test method of JIS K 0070, except that the temperature of the water bath is 95 ° C. and the heating time is 1 hour.

[Molecular weight of plasticizer and terminal alkyl esterification rate]
Molecular weight: In this specification, the molecular weight of a plasticizer means a number average molecular weight, and is calculated from the acid value, hydroxyl value and saponification value of the plasticizer according to the following formula.
Average molecular weight M = (M ₁ + M ₂ −M ₃ × 2) × n + M ₁ − (M ₃ −17.01) × 2 + (M ₃ −17.01) × p + (M ₂ −17.01) × q + 1.01 × (2−p −q)
q = Hydroxyl value × M ÷ 56110
2−p−q = acid value × M ÷ 56110
Average polymerization degree n = saponification number × M ÷ (2 × 56110) −1

Terminal alkyl esterification rate: The molecular terminal alkyl esterification rate (terminal alkyl esterification rate) can be calculated from the following formula. The larger the value of the molecular terminal alkyl esterification rate, the free carboxyl group or hydroxyl group There are few, and it shows that the molecular terminal is fully alkylesterified.
Terminal alkyl esterification rate (%) = (p ÷ 2) × 100
Where M _{1 is} the molecular weight of the dibasic acid ester
M ₂ : Molecular weight of dihydric alcohol
M ₃ : Molecular weight of monohydric alcohol p: Number of terminal alkyl ester groups in one molecule q: Number of terminal hydroxyl groups in one molecule In addition, when using multiple types of dicarboxylic acids, monohydric alcohols and dihydric alcohols, the molecular weight is The number average molecular weight is used.

Examples 1-12, Comparative Examples 1-5
Resin obtained in Production Examples 1 to 7, plasticizer obtained in Production Examples 1 to 3 of plasticizer, commercially available resin and commercially available plasticizer were mixed using a biaxial kneader at a blending ratio shown in Table 2. The mixture was kneaded at 200 ° C. to obtain a resin / plasticizer kneaded product as an adhesive.
Commercially available resins are those indicated by PLA, PBS and PHBH in Table 2, and commercially available plasticizers are those indicated by Plasticizer 4 in Table 2. The details of these commercial products are as follows.

PLA (polylactic acid): Nature Works LLC, Nature Works 4032D (melting point: 160 ° C.)
PBS (polybutylene succinate): manufactured by Showa Denko KK, Bionore 1001 (melting point: 110 ° C.)
PHBH (copolyester of 3-hydroxybutyric acid and R-3-hydroxyhexanoic acid): Kaneka Corporation, Aonilex (melting point: 145 ° C)
Plasticizer 1: Diester plasticizer of succinic acid and triethylene glycol monomethyl ether 2: Oligoester plasticizer of dimethyl succinate and diethylene glycol 3: Tris (ethoxyethoxyethyl) phosphate plasticizer 4: Adipic acid and diethylene glycol monomethyl ether / Diester with benzyl alcohol = 1/1 mixture (molar ratio), manufactured by Daihachi Chemical Industry Co., Ltd., DAIFATTY-101 (average molecular weight 338)

  As a plant-derived material used for the excrement disposal material, a crushed softwood crushed to 0.05 to 2 mm was used.

  The excrement disposal materials for pets of Examples 1 to 12 and Comparative Examples 1 to 5 were molded from the adhesive and the pulverized material. As a molding method, an extrusion molding machine capable of high-pressure extrusion installed so that the pressing rolls are adjacent to each other is used, and a crushed product of softwood and an adhesive (mass ratio: crushed softwood: adhesive) = 90: 10) was added, and compression extrusion molding granulation was performed at a temperature of 180 ° C. (a temperature equal to or higher than the melting point of the resin in the adhesive) to perform sizing. The pet excrement disposal material obtained had a columnar shape, and the particle size thereof was 4 mm in diameter and 10 mm in length.

About the obtained excrement disposal material for pets, the following evaluation was performed. The evaluation results are shown in Table 2.
(1) Heat-fusibility The pet excrement treating materials of the above Examples and Comparative Examples were immersed in 25 ° C. water for 10 seconds and then taken out. The thermal adhesiveness of the adhesive was evaluated from visual observation of the appearance of the pet excrement disposal material after immersion.

It is the same shape as before immersion. ... A (excellent)
The shape is slightly broken. ... B (good)
Half of the treated material is broken. ... C (Normal)
The treatment material has collapsed and does not retain its original shape. ... D (Inferior)

(2) Durability The pet excreta treating materials of the above Examples and Comparative Examples were stored at 40 ° C. and a humidity of 70% RH for 3 months. Subsequently, each processing material was evaluated by the same method and the same evaluation criteria as the above-mentioned heat fusibility.

[Discussion]
From the comparison of Examples 1 to 4, it was found that the use of the aliphatic diol having 10 to 12 carbon atoms makes the obtained adhesive more excellent in heat sealability and durability. From comparison between Examples 4 and 5, it was found that the aliphatic diol was more excellent in heat fusion and durability of the obtained adhesive than the aliphatic diamine was used. It was. From comparison between Examples 1 and 6 and Comparative Example 5, it was found that the durability was poor when the aliphatic dicarboxylic acid in the dicarboxylic acid component was 15 mol% or more.

  From the comparison between Examples 4 and 7 to 9, it was found that the heat-sealing property and durability of the adhesive were improved when a specific amount of the plasticizer was contained in the adhesive. From a comparison between Example 7 and Examples 4 and 10 to 12, it was found that a plasticizer having a predetermined structure improves the heat-fusability and durability of the adhesive. From Example 8 and Comparative Examples 2 to 4, it was suggested that when the dicarboxylic acid component in the resin does not contain a dicarboxylic acid having a furan ring, the adhesive is inferior in heat-fusibility and durability.

  The adhesive of the present invention is suitably used as an adhesive for articles that require hydrolysis resistance, such as pet excreta treating agents.

Claims (11)

An adhesive containing a resin,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. An adhesive which is a resin exceeding mol%, and the melting point of the resin is 50 ° C. or higher and 200 ° C. or lower. The resin is represented by the following general formula (1) or (2):

The adhesive according to claim 1, comprising a structural unit represented by the formula (wherein A represents an optionally substituted divalent aliphatic hydrocarbon group).   The adhesive according to claim 2, wherein the A is an alkylene group having 2 to 18 carbon atoms.   The adhesive according to any one of claims 1 to 3, further comprising 20 parts by mass or more and 200 parts by mass or less of a plasticizer with respect to 100 parts by mass of the resin.   The adhesive according to claim 4, wherein the plasticizer is an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms. The adhesive according to claim 4 or 5, wherein the plasticizer is at least one selected from the group consisting of the following ester compound (A), ester compound (B) and ester compound (C):
Compound (A): An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 2 to 3 alkylene oxides per hydroxyl group An ester compound which is an alcohol added with 5 to 5 moles,
Compound (B): Formula (I):
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 N represents a number from 1 to 12. All R ^{1 s} may be the same or different, all R ² may be the same or different, and all R ³ may be the same or different. An ester compound represented by:
Compound (C): Formula (II):

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms. Wherein x, y and z are each independently a positive number indicating the average number of moles added of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less.   The adhesive according to any one of claims 1 to 6, wherein a melt flow rate of the resin is 0.1 g / min or more and 80 g / min or less.   The adhesive according to any one of claims 1 to 7, which is for a wood material.     The excrement disposal agent for pets obtained by extruding and molding the adhesive according to any one of claims 1 to 8 and a pulverized material of a wood material at a temperature equal to or higher than the melting point of the resin in the adhesive.   A resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine and having an amount of a dicarboxylic acid compound having a furan ring in the dicarboxylic acid component exceeding 90 mol%. An adhesion method in which the resin has a melting point of 50 ° C. or higher and 200 ° C. or lower.   The bonding method according to claim 10, wherein the pulverized wood material is bonded.