JP5680449B2 - Cross-linking agent - Google Patents

Description

  The present invention is excellent in performance as a crosslinking agent, comprising a crosslinking agent containing a specific organoboron compound, a mixture obtained by mixing the crosslinking agent and a polymer having an active hydrogen-containing functional group, and a coating liquid comprising the mixture And a coating film formed by coating the same, a crosslinked product obtained by reacting the organoboron compound with a polymer having an active hydrogen-containing functional group, a resin composition containing the crosslinked product, the crosslinked product or the resin composition The present invention relates to a specific organoboron compound useful as a component constituting a molded article and a crosslinking agent.

  Since boric acid and its salts easily form a coordinate bond with a hydroxyl group by coordination exchange, it has been used for a long time as a curing agent or a crosslinking agent for a hydroxyl group-containing polymer in applications such as a binder (patents). See references 1 and 2). However, these conventional boric acid-based compounds sometimes have insufficient performance as a crosslinking agent, for example, a crosslinked product having desired physical properties cannot be obtained. In addition, conventional boric acid compounds are liable to be affected by the environment in the reaction system, such as a solvent, due to the coordination exchange properties as described above, and the potential drawback that the physical properties of the boric acid compounds change due to coordination exchange. have. For example, in the case of trimethyl borate in which all the substituents are substituted with methanol, the boiling point is lowered to 68 ° C. Therefore, when a conventional boric acid compound is blended with a hydroxyl group-containing polymer containing methanol and then molded, depending on the molding conditions, the boric acid compound volatilizes out of the system during processing. there were.

JP 2000-27093 A JP 2006-137078 A

  The present invention is excellent in performance as a cross-linking agent and is difficult to volatilize out of the system after blending, a mixture obtained by mixing the cross-linking agent and a polymer having an active hydrogen-containing functional group, and a coating comprising the mixture. A coating liquid formed by applying a working solution or a coating liquid, a crosslinked product obtained by reacting the organoboron compound and a polymer having an active hydrogen-containing functional group, a resin composition containing the crosslinked product, the crosslinked product, or the It aims at providing the organoboron compound useful as a component which comprises the molded object which consists of a resin composition, and a crosslinking agent.

  While the present inventors are variously examining the crosslinking agent, the organoboron compound having three or more specific partial structures containing a boron atom is excellent in performance as a crosslinking agent, and even when coordination exchange occurs. It was found that volatilization outside the system was suppressed, and further studies were made based on these findings to complete the present invention.

That is, the present invention
[1] A crosslinking agent containing an organoboron compound having three or more partial structures (I) represented by the following formula (I) in the molecule,

[In the formula (I), m represents 1 , n represents 3 , R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group, and R ¹ and R ² represent They may be bonded to each other. ]
[2] The crosslinking agent according to the above [1], wherein the organoboron compound has 3 to 6 partial structures (I) in the molecule,
[ 3 ] The organoboron compound is represented by the following formulas (a-3), (a-6), (a-9) and (a-12): (a-6), (a-6) ), (A-9) and (a-12), which is at least one member selected from the group consisting of (a-12),

[ 4 ] A mixture obtained by mixing any one of the above crosslinking agents [1] to [ 3 ] and a polymer having an active hydrogen-containing functional group,
[ 5 ] The mixture of the above [ 4 ], wherein the active hydrogen-containing functional group is a hydroxyl group,
[ 6 ] The polymer having an active hydrogen-containing functional group is a polyvinyl alcohol having a vinyl alcohol unit content of 80 mol% or more, an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%, and an acetal. The mixture of the above [ 4 ], which is at least one selected from the group consisting of polyvinyl acetals having a degree of conversion of 50 to 95 mol%,
[ 7 ] The mixture according to the above [ 4 ], wherein the polymer having an active hydrogen-containing functional group is a polyvinyl acetal having a degree of acetalization of 50 to 95 mol%.
[ 8 ] The mixture according to any one of [ 4 ] to [ 7 ], wherein a mixing ratio of the organoboron compound to 100 parts by mass of the polymer having an active hydrogen-containing functional group is 0.1 to 30 parts by mass.
[ 9 ] A mixture of any one of [ 4 ] to [ 8 ] above, comprising a liquid medium,
[1 0 ] A coating liquid comprising a mixture of the above [ 9 ],
[1 1 ] A coating film formed by applying the coating liquid of [1 0 ],
[1 2 ] A cross-linked product obtained by reacting the organoboron compound contained in any one of the above cross-linking agents [1] to [ 3 ] with a polymer having an active hydrogen-containing functional group,
[1 3 ] A crosslinked product of the above [1 2 ], wherein the active hydrogen-containing functional group is a hydroxyl group,
[1 4 ] The polymer having an active hydrogen-containing functional group is a polyvinyl alcohol having a vinyl alcohol unit content of 80 mol% or more, an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%, and The crosslinked product of the above [1 2 ], which is at least one selected from the group consisting of polyvinyl acetals having an acetalization degree of 50 to 95 mol%,
[1 5 ] The crosslinked product of [1 2 ] above, wherein the polymer having an active hydrogen-containing functional group is a polyvinyl acetal having a degree of acetalization of 50 to 95 mol%.
[1 6 ] Any one of the above [1 2 ] to [1 5 ], wherein 100 parts by mass of the polymer having an active hydrogen-containing functional group is reacted with 0.1 to 30 parts by mass of the organoboron compound. One cross-linked product,
[1 7 ] A resin composition comprising a crosslinked product of any one of the above [1 2 ] to [1 6 ],
[1 8 ] A molded product comprising the cross-linked product of any one of [1 2 ] to [1 6 ] or the resin composition of [1 7 ],
[ 19 ] An organoboron compound having three or more partial structures (I) represented by the following formula (I) in the molecule,

[In the formula (I), m represents 1 , n represents 3 , R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group, and R ¹ and R ² represent They may be bonded to each other. ]
[2 0 ] The organoboron compound according to the above [ 19 ], having 3 to 6 partial structures (I) in the molecule,
[2 1 ] Organic boron compounds (a-3), (a-6), (a-) represented by the following formulas (a-3), (a-6), (a-9) and (a-12) 9) and the organoboron compound of [ 19 ], which is any one of (a-12),

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About.

  According to the present invention, the cross-linking agent that is excellent in performance as a cross-linking agent and hardly volatilizes out of the system after blending, a mixture obtained by mixing the cross-linking agent and a polymer having an active hydrogen-containing functional group, from the mixture Coating solution formed by coating the same, a crosslinked product obtained by reacting the organoboron compound with a polymer having an active hydrogen-containing functional group, a resin composition containing the crosslinked product, and the crosslinked product Or the organic boron compound useful as a component which comprises the molded object and the crosslinking agent which consist of the said resin composition is provided.

It is a measurement result of the viscoelasticity of the film obtained in Examples 1 and 2 and Comparative Examples 1 and 2 of this specification.

[Crosslinking agent]
The crosslinking agent of the present invention contains an organoboron compound having three or more partial structures (I) represented by the following formula (I) in the molecule. Hereinafter, the organoboron compound may be referred to as “compound (a)”.

[In the formula (I), m represents 1 , n represents 3 , R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group, and R ¹ and R ² represent They may be bonded to each other. ]

In the partial structure (I), examples of the alkyl group before being substituted in the “optionally substituted alkyl group” represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group C1-C20 alkyl groups such as the above, and the viewpoint of volatility (easy removal by volatilization) of the leaving products after coordination substitution (typically R ¹ —OH and R ² —OH) Therefore, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group, an ethyl group, and an isopropyl group are more preferable.

Examples of the substituent in the “optionally substituted alkyl group” represented by each of R ¹ and R ² include aryl groups such as a phenyl group and a naphthyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom Etc. The number of substituents in the “optionally substituted alkyl group” is preferably in the range of 0 to 3, more preferably 0 or 1, and 0 (that is, the substituent is substituted). More preferably, it is an alkyl group that does not have.

R ¹ and R ² may be bonded to each other. When R ¹ and R ² are bonded to each other, a ring structure can be formed together with two oxygen atoms to which R ¹ and R ² are bonded and a boron atom to which the two oxygen atoms are bonded. When the partial structure (I) forms such a ring structure, the thermal stability of the resulting crosslinking agent is improved, so that the handleability is excellent. The bonding form of R ¹ and R ² is not particularly limited. For example, when both R ¹ and R ² are “optionally substituted alkyl groups”, these “optionally substituted alkyl groups” And a form corresponding to a structure in which one hydrogen atom is removed from each other and the hydrogen atoms are bonded to each other.

  Specific examples of the partial structure (I) include partial structures (I-1) to (I-12) represented by the following formulas (I-1) to (I-12).

  Among the above partial structures (I), the compound (a) can be easily prepared, and a cross-linking agent that is superior in solution stability and performance as a cross-linking agent when made into a solution can be obtained. -9) and partial structure (I-10) are preferred.

  Compound (a) has three or more partial structures (I) in the molecule. When the number of partial structures (I) is 2 or less, the performance as a crosslinking agent is insufficient. From the viewpoint of performance as a crosslinking agent, the compound (a) preferably has 3 to 6 partial structures (I) in the molecule, and more preferably 3 or 4. The partial structures (I) possessed by a plurality of compounds (a) may all be the same structure or may be partially or entirely different from each other, but are all the same because of easy production. A structure is preferred.

  In the compound (a), the structure of the portion other than the partial structure (I) (hereinafter sometimes referred to as “mother nucleus”) is not particularly limited, but as the mother nucleus, for example, the partial structure (I) is bonded. When a hydrogen atom is bonded to all of the moieties to be substituted, a mother nucleus that becomes an optionally substituted aliphatic hydrocarbon (including a mother nucleus that becomes an optionally substituted alicyclic hydrocarbon) is substituted. Examples thereof include a mother nucleus that becomes an aromatic hydrocarbon that may be included.

  Examples of the substituent in the above-mentioned “mother nucleus that becomes an optionally substituted aliphatic hydrocarbon” and “mother nucleus that becomes an optionally substituted aromatic hydrocarbon” include, for example, a hydroxyl group, an amino group, a carboxyl group, Examples include a sulfonic acid group, an amide group, a urethane group, a urea group, and a mercapto group. The number of substituents in “the mother nucleus that becomes an optionally substituted aliphatic hydrocarbon” and “the mother nucleus that becomes an optionally substituted aromatic hydrocarbon” is in the range of 0 to 3. Is preferable, and 0 or 1 is more preferable.

  The number of carbon atoms in the mother nucleus is preferably in the range of 1 to 10, and more preferably in the range of 2 to 6.

  Specific examples of the mother nucleus include mother nuclei (II-1) to (II-5) represented by the following formulas (II-1) to (II-5).

[In formulas (II-1) to (II-5), * represents a moiety to which partial structure (I) is bonded. ]

  Among the above mother nuclei, the mother nucleus (II-1) is preferable because the compound (a) having desired physical properties can be produced at low cost.

  If the molecular weight of the compound (a) is too small, the boiling point after the substituent on the boron atom is coordinated and exchanged with a lower alcohol or the like tends to decrease, and it tends to volatilize during molding. If it is too high, the solubility and the compatibility with the resin tend to decrease. Therefore, it is preferably in the range of 200 to 5000, more preferably in the range of 300 to 2500, and in the range of 500 to 1500. More preferably, it is within.

  Further, if the boron atom content in the compound (a) [the ratio of the mass of all boron atoms of the compound (a) to the mass of the compound (a)] is too low, the performance as a crosslinking agent is lowered. If it is too high, the solution stability at the time of making the solution tends to be poor, so it is preferably in the range of 1 to 15% by mass, and in the range of 2 to 10% by mass. Is more preferable, and it is still more preferable that it exists in the range of 3-7 mass%.

  Preferable specific examples of the compound (a) include, for example, organoboron compounds (a-1) to (a-15) represented by the following formulas (a-1) to (a-15).

  Among the above partial structures (I), the preparation of the compound (a) is easy, and a cross-linking agent that is superior in solution stability and performance as a cross-linking agent when made into a solution can be obtained. a-3), (a-6), (a-9), (a-12), and (a-15) are preferred, and the organoboron compounds (a-3), (a-6), and (a-9) ) And (a-12) are more preferable.

There is no restriction | limiting in particular in the manufacturing method of a compound (a), It can manufacture suitably by applying a well-known reaction. For example, in the partial structure (I), the compound (a) in which m is 1 and n is 3 is prepared in advance as a synthetic precursor in which allyloxy groups are bonded to all of the bonding parts of the partial structure (I). This can be easily produced by hydroboration reaction using a boron compound such as pinacol borane . Compound after manufacturing (a) can be optionally purified by techniques such as distillation.

  The crosslinking agent of this invention contains said compound (a). In the crosslinking agent of the present invention, only one type of compound (a) may be included, or two or more types may be included. Moreover, there is no restriction | limiting in particular in the content rate of the compound (a) in the crosslinking agent of this invention, Although it can adjust suitably according to a use etc., it is preferable to exist in the range of 50-100 mass%, 80- More preferably, it is in the range of 100% by mass, even more preferably in the range of 95-100% by mass, and the cross-linking agent may consist only of the compound (a). Examples of the component other than the compound (a) in the cross-linking agent include cross-linkable compounds other than the compound (a) such as boric acid and salts thereof; a filler; a stabilizer; a colorant;

  The specific use of the crosslinking agent of the present invention is not particularly limited as long as it is used for the purpose of crosslinking a compound, but it is preferably used for the purpose of crosslinking a polymer.

[Mixtures and cross-linked products]
The present invention includes a mixture obtained by mixing the above-described crosslinking agent and a polymer having an active hydrogen-containing functional group [hereinafter sometimes referred to as “polymer (b)”]. In the mixture, the compound (a) and the polymer (b) contained in the crosslinking agent react with each other due to the influence of mixing conditions, the presence or absence of a liquid medium described later, and the type of the crosslinking agent and polymer (b) used. A mode in which a part of the compound (a) and a part of the polymer (b) react to form a cross-linked product; a combination of the compound (a) and the polymer (b) An embodiment such as an embodiment in which all react to form a cross-linked product may be employed. In particular, when the mixture includes a liquid medium described later, at least a part of the compound (a) and the polymer (b) often exists as they are without reacting. Such a mixture can be preferably used as a coating liquid as described later. For example, the coating liquid is applied to an object to be coated such as a substrate, and further dried as necessary, whereby the compound (a) reacts with the polymer (b) and is obtained by the reaction. It is possible to easily form a coating film containing the resulting crosslinked product. In the partial structure (I) in the compound (a) contained in the cross-linking agent, the cross-linking agent and the polymer (b) are mixed, and in some cases, by further treatment such as coating and drying as described above. A functional group in which a hydrogen atom corresponding to active hydrogen is removed from an active hydrogen-containing functional group in the polymer (b) is bonded to the boron atom by coordination exchange, and as a result, the molecules of the polymer (b) are cross-linked. Thus, a crosslinked product is considered to be formed.

  There is no particular limitation on the mixing method in mixing the above crosslinking agent and the polymer (b). For example, a solution obtained by dissolving the crosslinking agent in a liquid medium and a polymer (b) in the liquid medium are dissolved. A solution in which a crosslinking agent is dissolved in a liquid medium and a polymer (b) pellet; a solution in which the crosslinking agent and the polymer (b) are dissolved in a liquid medium And a method of melt-kneading the crosslinking agent and the polymer (b) (polymer (b) pellets, etc.) using an extruder or the like in the presence of a plasticizer as necessary. Depending on the type of the polymer (b) and the use of the resulting mixture, it can be appropriately selected.

  There is no restriction | limiting in particular in the kind of said liquid medium, Water, a general purpose organic solvent, etc. can be used. Examples of general-purpose organic solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, ethylene glycol, diethylene glycol, hexylene glycol, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, γ-butyrolactone, ε-caprolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexane, toluene, acetonitrile and the like can be mentioned. A liquid medium may be used individually by 1 type, or may use 2 or more types together. Among these, water, methanol, ethanol, n-propanol, i-propanol, tetrahydrofuran, acetone, methyl ethyl ketone, hexane, since drying after coating is easy when using the above mixture as a coating liquid. Toluene and acetonitrile are preferred.

  The mixing ratio of the crosslinking agent and the polymer (b) can be appropriately adjusted according to the purpose of use of the final product such as the coating film or the molded product described later, but the stability of the resulting mixture or final product can be adjusted. From the viewpoint of properties and the like, the ratio of the compound (a) contained in the cross-linking agent to 100 parts by mass of the polymer (b) is preferably in the range of 0.1 to 30 parts by mass, and 0.2 to 20 More preferably within the range of parts by mass, even more preferably within the range of 0.5 to 10 parts by mass. By mixing the crosslinking agent and the polymer (b) at the above mixing ratio, a crosslinked product obtained by reacting the compound (a) and the polymer (b) at the above ratio can be easily obtained.

  The type of the active hydrogen-containing functional group that the polymer (b) has is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, an amide group, a urethane group, a urea group, and a mercapto group. (B) may have only one type of active hydrogen-containing functional group or may have two or more types of active hydrogen-containing functional groups. The active hydrogen-containing functional group is preferably a hydroxyl group, an amino group, or a carboxyl group, more preferably a hydroxyl group or a carboxyl group, and particularly preferably a hydroxyl group because it can easily give a crosslinked product. preferable.

  In the polymer (b), the active hydrogen-containing functional group may have at least a part of the repeating unit constituting the polymer (b), or may have an end of the polymer (b). It is preferable that at least a part of the repeating units constituting the polymer (b) have a cross-linked product easily. When at least a part of the repeating unit constituting the polymer (b) has, even if the active hydrogen-containing functional group is contained in the side chain of the repeating unit having the same, the entire side chain is active. Including the case of a hydrogen-containing functional group], it may be contained in the main chain of the repeating unit, but it is preferred that it is contained in the side chain because a crosslinked product can be easily provided.

  Specific examples of the polymer (b) include, for example, polyvinyl alcohol polymers, polyacrylic acid, polyamide, polyurethane, ionomer and the like. A polymer (b) may be used individually by 1 type, or may use 2 or more types together. Among these polymers (b), a polyvinyl alcohol polymer is preferable, and in particular, polyvinyl alcohol having a vinyl alcohol unit content of 80 mol% or more [hereinafter sometimes referred to as polymer (b-1)], An ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol% [hereinafter sometimes referred to as polymer (b-2)], and a polyvinyl acetal having an acetalization degree of 50 to 95 mol% [hereinafter, At least one selected from the group consisting of [sometimes referred to as polymer (b-3)] is more preferred, and polymer (b-3) is more preferred.

  The polyvinyl alcohol polymer is usually obtained by polymerizing a vinyl ester typified by vinyl acetate alone or, if necessary, with another monomer other than the vinyl ester to obtain a polyvinyl ester polymer. Can be produced by saponification with an acidic substance or an alkaline substance. Here, the content rate of a vinyl alcohol unit can be made into a desired range by adjusting the usage-amount of said other monomer, and the grade of saponification. Further, when an appropriate amount of ethylene is used as at least a part of the other monomer, an ethylene-vinyl alcohol copolymer having a desired ethylene content can be obtained. Furthermore, if a part of the hydroxyl group generated by saponification is acetalized with an aldehyde or a derivative thereof, a polyvinyl acetal having a desired degree of acetalization can be obtained.

  The content of vinyl alcohol units in the polymer (b-1) [ratio of the number of moles of vinyl alcohol units to the number of moles of all structural units constituting the polymer (b-1)] is the processability of the resulting crosslinked product. In view of the above, it is 80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more. Although there is no restriction | limiting in particular in the upper limit of the content rate of the vinyl alcohol unit of a polymer (b-1), From viewpoints, such as the ease of preparation of a polymer (b-1), the said content rate is 99.9 mol% or less. It is preferable that

  Further, the degree of polymerization of the polymer (b-1) is preferably in the range of 300 to 5000, more preferably in the range of 400 to 3000, from the viewpoint of viscosity stability when it is made into a solution. More preferably, it is in the range of 500-2500. In the present specification, the degree of polymerization of the polymer (b-1) means an average degree of polymerization measured according to the description of JIS K6726-1994, and the polymer (b-1) is re-saponified and purified. Then, it can be determined from the intrinsic viscosity measured in 30 ° C. water.

  The ethylene content in the polymer (b-2) [ratio of the number of moles of ethylene units to the number of moles of all structural units constituting the polymer (b-2)] is 20 from the viewpoint of processability of the resulting crosslinked product. It is within the range of ˜50 mol%, preferably within the range of 25 to 45 mol%, and more preferably within the range of 30 to 40 mol%.

  The content of vinyl alcohol units in the polymer (b-2) [ratio of the number of moles of vinyl alcohol units to the number of moles of all structural units constituting the polymer (b-2)] is the processability of the resulting crosslinked product. In view of the above, it is preferably in the range of 40 to 80 mol%, more preferably in the range of 45 to 75 mol%, and still more preferably in the range of 50 to 70 mol%.

  In addition, the melt flow rate (measured according to the description of ASTM D1238 under conditions of a temperature of 190 ° C. and a load of 2.16 kg) of the polymer (b-2) is within a range of 0.1 to 100 g / 10 minutes. It is preferably within a range of 0.2 to 50 g / 10 minutes, and more preferably within a range of 0.5 to 20 g / 10 minutes.

  Examples of the aldehyde or derivative thereof used for the production of the polymer (b-3) include aldehydes such as formaldehyde, acetaldehyde, n-butyraldehyde, benzaldehyde; acetals of these aldehydes; vinyl ethers prepared from these aldehydes Of these, one of these may be used alone, or two or more may be used in combination. Among these, since manufacture of a polymer (b-3) is easy, formaldehyde, acetaldehyde, and n-butyraldehyde are preferable, and n-butyraldehyde is more preferable.

  If the degree of acetalization of the polymer (b-3) is too low, the availability tends to be difficult or the melt processability tends to be poor. On the other hand, if it is too high, the availability tends to be difficult. Therefore, it is within the range of 50 to 95 mol%, preferably within the range of 55 to 90 mol%, and more preferably within the range of 60 to 85 mol%. In the present specification, the degree of acetalization means the ratio of the number of moles of the structural unit constituting the acetal unit to the total number of moles of the structural unit constituting the acetal unit, the vinyl alcohol unit and the vinyl ester unit. Here, since one acetal unit is considered to be formed from two structural units, the number of moles of the structural unit constituting the acetal unit is usually twice the number of moles of the acetal unit.

  The content of vinyl alcohol units in the polymer (b-3) [ratio of the number of moles of vinyl alcohol units to the number of moles of all structural units constituting the polymer (b-3)] is 3 from the viewpoint of productivity. It is preferably in the range of ˜50 mol%, more preferably in the range of 5 to 45 mol%, and further preferably in the range of 10 to 40 mol%. In the present specification, when the polymer contains an acetal unit, the number of moles of all the structural units of the polymer is determined on the basis of the number of structural units constituting the acetal unit. That is, when one acetal unit is composed of two vinyl alcohol units, the number of moles of all the structural units of the polymer is determined on the basis of the number of moles of the vinyl alcohol unit constituting the acetal unit. And

  The degree of polymerization of the polymer (b-3) is preferably in the range of 300 to 4000 and in the range of 400 to 3000 in the state before acetalization from the viewpoint of moldability and mechanical properties. Is more preferable, and it is further preferable to be within the range of 500-2500. In this specification, the degree of polymerization of the polymer (b-3) in the state before acetalization means the average degree of polymerization measured according to the description of JIS K6726-1994, and the weight before acetalization. It can be determined from the intrinsic viscosity measured in 30 ° C. water after re-saponifying and purifying the coalescence (b-3).

[Coating fluid and coating film]
As described above, a mixture containing a liquid medium can be preferably used as a coating liquid. Examples of the coating liquid include a solution in which components other than the liquid medium, such as the plasticizer, the polymer (b), and a cross-linked product obtained by reacting them, are completely dissolved in the liquid medium, and other than the liquid medium. And a dispersion in which at least a part of the components is dispersed in a liquid medium. Among these, a solution in which components other than the liquid medium are dissolved in the liquid medium is preferable because uniform coating is possible.

  The coating liquid contains other components in addition to the compound (a), the polymer (b), the cross-linked product obtained by reacting these and the liquid medium, depending on the intended use of the resulting coating film. be able to. Examples of such other components include antioxidants, stabilizers, lubricants, flame retardants, processing aids, antistatic agents, colorants, heat ray reflective agents, heat ray absorbents, impact aids, fillers, Examples thereof include a moisture-resistant agent, a dispersant, a surfactant, an ultraviolet absorber, and a polymer other than the polymer (b), and one or more of these can be included. The proportion of the total mass of the compound (a), the polymer (b) and the cross-linked product obtained by reacting these with respect to the total mass of components other than the liquid medium contained in the coating liquid is 50% by mass or more. It is preferably 80% by mass or more, more preferably 95% by mass or more, and may be 100% by mass.

  The ratio of the total mass of components other than the liquid medium contained in the coating liquid to the total mass of the coating liquid varies depending on the application, but if it is too low, it takes a long time to dry after coating. If the viscosity is too high, the viscosity tends to be high and the workability during coating tends to be reduced. Therefore, it is preferably in the range of 1 to 40% by mass, and 2 to 30% by mass. More preferably, it is in the range, and further preferably in the range of 2.5 to 20% by mass.

  There is no particular limitation on the preparation method of the coating liquid, and a mixture containing a liquid medium obtained by mixing the crosslinking agent and the polymer (b) as described above may be used as it is as the coating liquid. A liquid medium or the like further added to the obtained mixture or a part of the liquid medium removed from the obtained mixture by evaporation or the like may be used as the coating liquid.

  Although there is no restriction | limiting in particular in the use of a coating liquid, For example, a ceramic binder, ink, etc. are mentioned. The coating object to which the coating liquid is applied depends on the application, and examples thereof include ceramics and synthetic resin sheets.

[Resin composition]
Although the above-mentioned crosslinked product may be used alone, it may be used as a resin composition containing a crosslinked product and other components depending on applications. In addition, when the crosslinking agent and the polymer (b) are mixed to obtain a crosslinked product, in addition to the crosslinked product, an unreacted compound (a), an unreacted polymer (b), and a decomposition product of the crosslinking agent. In some cases, a crude product containing the above components may be obtained. However, if these components are used without being removed, the purification work of the cross-linked product becomes unnecessary.
Examples of components other than the cross-linked product in the resin composition include, for example, a liquid medium, an antioxidant, a stabilizer, a lubricant, a flame retardant, a processing aid, an antistatic agent, a colorant, a heat ray reflective agent, a heat ray absorbent, Impact-resistant auxiliary agent, filler, moisture-resistant agent, dispersant, surfactant, ultraviolet absorber, polymer other than polymer (b), unreacted compound (a), unreacted polymer ( b), decomposition products of the above-mentioned crosslinking agents, and the like, and one or more of these may be included depending on the application.

[Molded body]
As an example of the preferable form of said crosslinked material or a resin composition containing it, the molded object which consists of said crosslinked material or a resin composition containing it is mentioned. There is no restriction | limiting in particular in the specific form of a molded object, For example, a film, a sheet | seat, a fiber, various three-dimensional structures etc. are mentioned. Moreover, the form of the pellet used in order to manufacture another molded object may be sufficient.

  There is no particular limitation on the method for producing the molded body, for example, a method of obtaining the molded body as a coating film by applying the above coating liquid to a coating object such as a substrate and further drying as necessary. A cross-linking agent and a polymer (b) (such as pellets of the polymer (b)) are melt-kneaded using an extruder in the presence of a plasticizer, if necessary, and then extruded from various dies to obtain an extruded molded body. Method of obtaining; Method of obtaining an injection-molded product by supplying a crosslinking agent and a polymer (b) (such as pellets of polymer (b)) together with a plasticizer to an injection molding machine; Crosslinking agent and polymer Examples thereof include a method of hot pressing a mixture obtained by mixing (b) with a plasticizer as necessary to obtain a film-like or sheet-like molded article. In particular, the above-described cross-linked product is intended to be used even when a molded body is produced by a method including a step of melt-kneading because the cross-linked product is fluid even when heated to a higher temperature. It becomes possible to manufacture a molded body easily.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In addition, the measuring method of the viscoelasticity of the film employ | adopted in the following examples and comparative examples was shown below.

[Measurement method of viscoelasticity of film]
A measurement sample having a size of 30 mm × 5 mm was cut out from the film obtained in the following Examples or Comparative Examples, and the storage elastic modulus E ′ was obtained using a dynamic viscoelasticity measuring device “DVE-V4” manufactured by UBM Co., Ltd. Was measured. The measurement was performed in a temperature range of −35 ° C. to 220 ° C. under conditions of a temperature rising rate of 3 ° C./min and a frequency of 10 Hz.

[Example 1]
Synthesis of organoboron compound (a-3)

In a reactor, 4.6 parts by mass of glycerin, 20 parts by mass of sodium hydroxide, 5.8 parts by mass of tetrabutylammonium bromide, and 20 parts by mass of water were stirred, and then 27.6 parts by mass of allyl chloride was added thereto. The mixture was stirred at 60 ° C. for 12 hours. Ethyl acetate and saturated brine were added to the obtained mixture and the mixture was stirred and separated. The organic layer was concentrated and distilled under reduced pressure to give glyceryl triallyl ether. The analysis results of ¹ H-NMR of the obtained glycerin triallyl ether are shown below.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ (ppm): 3.5-3.6 (4H, OCCH H ₂ O), 3.65-3.75 (1H, OC H CH ₂ O), _{4.0-4.1 (4H, CH 2 OC H} 2 CH = CH 2), 4.1-4.2 (2H, CHOC H 2 CH = CH 2), 5.1-5.3 (6H, _{OCH 2 CH = C H 2)} , 5.8-6.0 (3H, OCH 2 C H = CH 2)

In a separate reactor, 1.75 parts by mass of tris (triphenylphosphine) rhodium chloride, 84 parts by mass of tetrahydrofuran and 8.7 parts by mass of pinacolborane were added, and 4.0 parts by mass of the above glyceryl triallyl ether was added thereto. After stirring at room temperature for 1 hour, the mixture was further heated to reflux for 1 hour. Ethyl acetate and water were added to the obtained mixture and the mixture was stirred and separated. The organic layer was concentrated and distilled under reduced pressure to obtain an organic boron compound (a-3). The analysis result of ¹ H-NMR of the obtained organic boron compound (a-3) is shown below.

^{1 H-NMR (270MHz, DMSO} -d 6, TMS) δ (ppm): 0.9-1.0 (6H, CH 2 C H 2 B), 1.27 (36H, BOCC H 3), 1. _{5-1.7 (6H, OCH 2 C H} 2 CH 2 B), 3.3-3.6 (11H, OC H 2 CH 2 CH 2 B, OCHC H 2 O, OC H CH 2 O)

Preparation of coating solution Using the organoboron compound (a-3) as a crosslinking agent, a coating solution was prepared by mixing this with polyvinyl butyral. That is, polyvinyl butyral (polyvinyl alcohol having a polymerization degree of 600 acetalized with n-butyraldehyde. Degree of acetalization: 63.5 mol%, vinyl alcohol unit content: 35 mol%, vinyl acetate unit content: 1.5 mol%) is added to 8.5 parts by mass of a 10% by mass ethanol solution, and 8.5 parts by mass of an ethanol solution in which 0.026 parts by mass of the organic boron compound (a-3) is dissolved. A uniform coating solution was obtained by stirring.

Preparation of Film The above coating solution was poured into a PET film mold processed to a size of 10 cm × 10 cm, and the solvent was sufficiently evaporated, followed by vacuum drying at room temperature for 24 hours to prepare a film. Viscoelasticity was evaluated by the above method using the obtained film. The results are shown in FIG.

[Example 2]
Synthesis of organoboron compound (a-12)

A reactor is charged with 50 parts by mass of pentaerythritol triallyl ether, 36 parts by mass of sodium hydroxide, 7.0 parts by mass of tetrabutylammonium bromide, and 36 parts by mass of water. And stirred at 60 ° C. for 9 hours. Ethyl acetate and saturated brine were added to the obtained mixture and the mixture was stirred and separated. The organic layer was concentrated and distilled under reduced pressure to obtain pentaerythritol tetraallyl ether. The results of ¹ H-NMR analysis of the resulting pentaerythritol tetraallyl ether are shown below.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ (ppm): 3.47 (8H, CC H ₂ O), 3.9-4.0 (8H, OC H ₂ CH═CH ₂ ), 5. _{1-5.3 (8H, OCH 2 CH =} C H 2), 5.8-6.0 (4H, OCH 2 C H = CH 2)

In another reactor, 1.5 parts by mass of tris (triphenylphosphine) rhodium chloride, 88.4 parts by mass of tetrahydrofuran and 17.7 parts by mass of pinacolborane were added, and 10.0 parts by mass of the above-mentioned pentaerythritol tetraallyl ether was added thereto. After stirring at room temperature for 1 hour, the mixture was further heated to reflux for 1 hour. Ethyl acetate and water were added to the obtained mixture and the mixture was stirred and separated. The organic layer was concentrated and distilled under reduced pressure to obtain an organic boron compound (a-12). The analysis result of ¹ H-NMR of the obtained organic boron compound (a-12) is shown below.

_{^{1 H-NMR (270MHz, DMSO}} -d 6, TMS): 0.85-0.95 (8H, CH 2 C H 2 B), 1.27 (48H, BOCC H 3), 1.5-1. _{7 (8H, OCH 2 C H} 2 CH 2 B), 3.3-3.5 (16H, CC H 2 O, OC H 2 CH 2 CH 2 B)

Preparation of coating liquid and production of film In Example 1, except that 0.026 parts by mass of organic boron compound (a-12) was used instead of 0.026 parts by mass of organic boron compound (a-3). A coating solution was prepared in the same manner as in Example 1. Using this coating solution, a film was produced in the same manner as in Example 1, and viscoelasticity was evaluated by the above method. The results are shown in FIG.

[Comparative Example 1]
In Example 1, Example 1 was used except that 8.5 parts by mass of ethanol in which the organic boron compound was not dissolved was used instead of 8.5 parts by mass of the ethanol solution in which the organic boron compound (a-3) was dissolved. A coating solution was prepared in the same manner as described above. Using this coating solution, a film was produced in the same manner as in Example 1, and viscoelasticity was evaluated by the above method. The results are shown in FIG.

[Comparative Example 2]
In Example 1, the coating liquid was prepared like Example 1 except having used 0.026 mass part of boric acid instead of 0.026 mass part of organoboron compound (a-3). Using this coating solution, a film was produced in the same manner as in Example 1, and viscoelasticity was evaluated by the above method. The results are shown in FIG.

  As is apparent from FIG. 1, the film obtained using the crosslinking agent of the present invention has a small decrease in storage elastic modulus in the high-temperature rubber region and is excellent in performance as a crosslinking agent.

Claims (21)

The crosslinking agent containing the organoboron compound which has 3 or more in partial molecule | numerator (I) shown by following formula (I).

[In the formula (I), m represents 1 , n represents 3 , R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group, and R ¹ and R ² represent They may be bonded to each other. ] The crosslinking agent according to claim 1, wherein the organoboron compound has 3 to 6 partial structures (I) in the molecule. The organoboron compound is represented by the following formulas (a-3), (a-6), (a-9) and (a-12): (a-3), (a-6), ( The crosslinking agent of Claim 1 which is at least 1 sort (s) chosen from the group which consists of a-9) and (a-12).

A mixture obtained by mixing the crosslinking agent according to any one of claims 1 to 3 and a polymer having an active hydrogen-containing functional group. The mixture according to claim 4 , wherein the active hydrogen-containing functional group is a hydroxyl group. The polymer having an active hydrogen-containing functional group is a polyvinyl alcohol having a vinyl alcohol unit content of 80 mol% or more, an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%, and an acetalization degree. The mixture of Claim 4 which is at least 1 sort (s) chosen from the group which consists of 50-95 mol% polyvinyl acetal. The mixture according to claim 4 , wherein the polymer having an active hydrogen-containing functional group is polyvinyl acetal having a degree of acetalization of 50 to 95 mol%. The mixing ratio of the organic boron compound to the polymer 100 parts by mass having an active hydrogen-containing functional group is 0.1 to 30 parts by weight, the mixture according to any one of claims 4-7. The mixture according to any one of claims 4 to 8 , comprising a liquid medium. A coating liquid comprising the mixture according to claim 9 . The coating film formed by coating the coating liquid of Claim 10 . A crosslinked product obtained by reacting the organoboron compound contained in the crosslinking agent according to any one of claims 1 to 3 and a polymer having an active hydrogen-containing functional group. The active hydrogen-containing functional group is a hydroxyl group, crosslinked product of claim 1 2. The polymer having an active hydrogen-containing functional group is a polyvinyl alcohol having a vinyl alcohol unit content of 80 mol% or more, an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%, and an acetalization degree. it is at least one selected from the group consisting of 50 to 95 mole% of polyvinyl acetal, crosslinked product of claim 1 2. It said polymer having active hydrogen-containing functional groups, the degree of acetalization is 50 to 95 mole percent of polyvinyl acetal, crosslinked product of claim 1 2. A polymer 100 parts by mass having an active hydrogen-containing functional groups, said comprising an organic boron compound 0.1 to 30 parts by weight are reacted, crosslinked product according to any one of claims 1 2 to 1 5 . Resin composition comprising a crosslinked product according to any one of claims 1 2 to 1 6. A molded article comprising the crosslinked product according to any one of claims 12 to 16 or the resin composition according to claim 17 . An organoboron compound having three or more partial structures (I) represented by the following formula (I) in the molecule.

[In the formula (I), m represents 1 , n represents 3 , R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group, and R ¹ and R ² represent They may be bonded to each other. ] The organoboron compound according to claim 19 , which has 3 to 6 partial structures (I) in the molecule. Organoboron compounds (a-3), (a-6), (a-9) and (a) represented by the following formulas (a-3), (a-6), (a-9) and (a-12) The organoboron compound according to claim 19 , which is any one of a-12).

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