JPH06345978A - Crosslinking agent, polymer composition, crosslinking method, and crosslinked object - Google Patents

Abstract

PURPOSE:To obtain a polymer composition which is capable of forming a crosslinked object excellent in resistances to heat, water, and oil, solvent insolubility, etc., by incorporating a crosslinking agent comprising a compound having a specific structure into a polymer having a functional group containing active hydrogen. CONSTITUTION:A crosslinking agent comprising a bicyclic amideacetal compound which is represented by the formula [wherein R<1> to R<9> each is H, a halogen, a preferably 1-5C alkyl (substituted with OH, a halogen, etc.), an aryl, a preferably 1-5C alkoxy, or phenoxy] [which may be a dimer comprising two bicycle amideacetal moieties bonded through a divalent group (e.g. an alkylene or arylene)] is incorporated into a polymer having a functional group containing active hydrogen to obtain a polymer composition. The polymer can be crosslinked with this crosslinking agent without generating formalin, thereby giving a crosslinked object excellent in resistances to heat, water, and oil, solvent insolubility, etc. The composition containing the crosslinking agent can hence be advantageously used in the fields of textile processing, baking paints, heat-resistant adhesives, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crosslinking agent, a polymer composition, a crosslinking method and a crosslinked body. More specifically, a cross-linking agent capable of cross-linking a polymer without generating formalin, a polymer composition containing the same, a cross-linking method using the cross-linking agent and heat resistance, water resistance, solvent solubility resistance, oil resistance. The present invention relates to a crosslinked product having excellent properties.

[0002]

Polymer compositions containing a polymer and a cross-linking agent are widely used in the fields of fiber processing, baking coatings, heat-resistant adhesives and the like. By crosslinking the polymer in such a polymer composition, a crosslinked product excellent in heat resistance, water resistance, solvent solubility resistance, oil resistance and the like can be obtained. Heretofore, melamine, methylol urea and the like have been known as crosslinking agents. These cross-linking agents are used by being blended with a (meth) acrylic acid ester polymer and the like, but it is necessary to heat the polymer to a high temperature of 130 ° C. or higher in order to cross-link the polymer, and at the time of cross-linking, formalin is used. May occur. There is also a method of adding an acid catalyst in order to lower the temperature for crosslinking, but there is a problem that a commonly used acid catalyst is highly toxic and the pot life of the polymer composition is shortened.

[0003]

The object of the present invention is to provide a novel cross-linking agent capable of cross-linking a polymer without generating formalin, a polymer composition containing the same, and a cross-linking method using the cross-linking agent. And to provide a crosslinked product having excellent heat resistance, water resistance, solvent solubility resistance, oil resistance, and the like. As a result of intensive studies aimed at achieving the above object, the present inventors have found that this object can be achieved by using a compound having a specific structure as a crosslinking agent, and have completed the present invention.

[0004]

Thus, according to the present invention, there is provided a crosslinking agent comprising a bicyclic amide acetal. Further, according to the present invention, there is provided a polymer composition containing the cross-linking agent and a polymer having an active hydrogen-containing functional group. Further, there is provided a method for crosslinking a polymer having an active hydrogen-containing functional group characterized by using the above-mentioned crosslinking agent, and a crosslinked body obtained by this method.

The cross-linking agent of the present invention comprises a bicyclic amide acetal.

The bicyclic amide acetal used in the present invention is a compound represented by the formula (1).

[0007]

[Chemical 1]

R ^{1 to} R ⁹ in the formula (1) are each independently a hydrogen atom, a halogen group, an alkyl group, an aryl group, an alkoxy group or a phenoxy group, and n and m are each independently 1 or 2. is there. The alkyl group, aryl group, alkoxy group or phenoxy group includes those in which a hydrogen atom in these groups is substituted with a hydroxyl group, a halogen group or the like. The alkyl group and the alkoxy group preferably have 1 to 5 carbon atoms. In addition, the bicyclic amide acetal is
It includes a dimer in which two bicyclic amide acetals are bound to each other via a divalent group. Examples of the divalent group include an alkylene group, an arylene group, an alkyleneoxy group, an aryleneoxy group, an imino group, an oxygen atom or a sulfur atom.

Specific examples of the bicyclic amide acetal include 5-methyl-3-phenoxymethyl-1-aza-
4,6-Dioxabicyclo [3,3,0] octane, 5
-Ethyl-3-phenyl-1-aza-4,6-dioxabicyclo [3,3,0] octane, 5-ethyl-3-allyloxymethyl-1-aza-4,6-dioxabicyclo [3 , 3,0] octane, 1-aza-4,6-dioxabicyclo [3,3,0] octane, 3,5-diphenyl-1-aza-4,6-dioxabicyclo [3,3,3]
0] octane, 6-methyl-8-phenyl-1-aza-
5,7-Dioxabicyclo [4,3,0] nonane, 4-
Ethyl-8-phenoxymethyl-6-phenyl-1-aza-5,7-dioxabicyclo [4,3,0] nonane,
1,4-bis [5-ethyl-1-aza-4,6-dioxabicyclo [3,3,0] octan-3-ylmethyloxy] butane and the like can be mentioned.

The polymer composition of the present invention contains the crosslinking agent of the present invention and a polymer having an active hydrogen-containing functional group.

The polymer used in the polymer composition of the present invention is
A polymer having an active hydrogen-containing functional group. The active hydrogen-containing functional group includes a functional group which is hydrolyzed to generate an active hydrogen-containing functional group. Active hydrogen is an oxygen atom,
A highly reactive hydrogen atom bonded to a nitrogen atom or a sulfur atom. Specific examples of the active hydrogen-containing functional group include amino group, imino group, carboxyl group, acid anhydride group, phenolic hydroxyl group, sulfo group and thiol group. Particularly, a carboxyl group is preferable because it has high reactivity with the crosslinking agent of the present invention.

The amount of the active hydrogen-containing functional group in the polymer having the active hydrogen-containing functional group is usually 0.01 meq or more, preferably 0.1 to 4 per 1 g of the polymer.
It is a milliequivalent. If the amount is less than 0.01 meq, the degree of cross-linking becomes low and the solvent solubility of the polymer may not be improved.

The polymer having an active hydrogen-containing functional group is not particularly limited by its synthetic method. For example, it is obtained by polymerizing a monomer having an active hydrogen-containing functional group alone or a monomer having an active hydrogen-containing functional group and a monomer copolymerizable therewith.

Examples of the monomer having an active hydrogen-containing functional group include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, ethylenically unsaturated carboxylic acid monomers such as monoethyl maleate; (meth) acrylamide. , N-methylol (meth) acrylamide and other ethylenically unsaturated amide monomers; vinylethylamine, vinylbutylamine and other ethylenically unsaturated amine monomers; styrene sulfonic acid and other ethylenically unsaturated sulfonic acid monomers Is mentioned. Particularly, an ethylenically unsaturated carboxylic acid monomer is suitable.

Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like; (meth) acrylic acid can be used as the monomer copolymerizable with the monomer having an active hydrogen-containing functional group. Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate,
Ethylenically unsaturated carboxylic acid ester monomers such as hexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, diethyl maleate and dimethyl itaconate; vinyl cyanide such as (meth) acrylonitrile Monomer; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3
-Conjugated diene monomers such as pentadiene; vinyl halide monomers such as vinyl chloride; carboxylic acid vinyl ester monomers such as vinyl acetate.

The method of polymerizing the monomer having an active hydrogen-containing functional group alone or the method of polymerizing a monomer having an active hydrogen-containing functional group and a monomer copolymerizable therewith is not particularly limited.
For example, an emulsion polymerization method, a solution polymerization method, and a suspension polymerization method can be mentioned.

The polymer having an active hydrogen-containing functional group can also be obtained by adding a compound having an active hydrogen-containing functional group to the polymer chain of the polymer.

The polymer to which the compound having an active hydrogen-containing functional group is added has a reaction site for the addition of the compound having an active hydrogen-containing functional group to the polymer. Examples of the reaction point include a carbon-carbon double bond, a carboxyl group and an epoxy group. Specific examples of the polymer to which the compound having an active hydrogen-containing functional group is added include aromatic vinyl monomer-conjugated diene monomer-based copolymer, vinyl cyanide monomer-conjugated diene monomer-based copolymer. , Carboxy-modified ethylenically unsaturated carboxylic acid ester-based polymers and the like.

As the compound having an active hydrogen-containing functional group, a compound containing a hydrogen atom bonded to an oxygen atom such as acrylic acid, methacrylic acid or maleic acid; ammonia,
Examples thereof include compounds containing a hydrogen atom bonded to a nitrogen atom such as alkylimine and polyvalent amine.

The method for adding a compound having an active hydrogen-containing functional group to the polymer chain of the polymer is not particularly limited, and for example, a polymer having a carbon-carbon unsaturated bond may be added with an ethylenically unsaturated carboxylic acid or the like. Method for adding EN; JP-A-63
-56549 and JP-A-62-17601, a method of adding an alkylimine or a polyvalent amine to a polymer having a carboxyl group; JP-A-61-1
As described in Japanese Patent No. 36515, there is a method of adding ammonia to a polymer having an epoxy group.

The ratio of the cross-linking agent of the present invention to the polymer having an active hydrogen-containing functional group is 1 mole of the active hydrogen-containing functional group in the polymer and the bicyclic amide acetal as the cross-linking agent. Is usually 0.01 to 20 mol, preferably 0.1 to 10 mol. When the amount of the bicyclic amide acetal is less than 0.01 mol, the degree of cross-linking is low, and the solvent resistance of the cross-linked product may not be improved. Even if it exceeds 20 moles, the degree of crosslinking does not exceed a certain value.

The polymer composition of the present invention is not particularly limited depending on its properties and may be, for example, a solution, a dispersion, a solid or the like.

The polymer composition of the present invention is not particularly limited by its preparation method. For example, a method in which the crosslinking agent and the emulsifier of the present invention are added to water and stirred to obtain a dispersion, and the dispersion is added to a latex of a polymer having an active hydrogen-containing functional group and stirred; the polymer is an organic solvent. Method of adding the cross-linking agent of the present invention and stirring after dissolving it in a solution; Method of adding and kneading the cross-linking agent of the present invention while kneading the polymer with a roll or the like; synthesizing polymer having active hydrogen-containing functional group At this time, any method such as a method of adding the crosslinking agent of the present invention to the reactor may be used. The latex of a polymer having an active hydrogen-containing functional group is preferably adjusted to have a pH of 2 or more, particularly 2 to 10, before the addition of a crosslinking agent to the latex. If the pH is too low, the latex may aggregate. When the cross-linking agent of the present invention is added to the reactor to synthesize a polymer having an active hydrogen-containing functional group, the synthesis temperature is lower than room temperature, preferably less than 20 ° C. When the synthesis temperature is high, the pot life of the resulting polymer composition may be shortened.

The crosslinked product of the present invention is obtained by crosslinking a polymer having an active hydrogen-containing functional group with the crosslinking agent of the present invention. Crosslinking conditions are not particularly limited. For example, it can be obtained by heating the polymer composition of the present invention. The heating temperature is usually 30 to 200 ° C, preferably 80 to 150 ° C. The heating time is usually 3 to 3
0 minutes. When the heating temperature is low or the heating time is short, the solvent solubility of the crosslinked product may not be improved. On the contrary, even if the heating temperature is increased or the heating time is increased, the degree of crosslinking does not exceed a certain value.

Although it is not known how the cross-linking agent of the present invention reacts with the polymer having an active hydrogen-containing functional group to cross-link the polymer, the bicyclic amide acetal as the cross-linking agent and the polymer It is believed that a crosslink is formed by forming a bridge bond with the active hydrogen-containing functional group of and the polymer is crosslinked.

[0026]

According to the present invention, a cross-linking agent capable of cross-linking a polymer without generating formalin, a polymer composition containing the cross-linking agent, a cross-linking method using the cross-linking agent, and heat resistance and water resistance. It is possible to provide a crosslinked product having excellent chemical resistance, solvent resistance and the like. Since the cross-linking agent of the present invention does not generate formalin when the polymer is cross-linked, the polymer composition containing this can be suitably used in the fields of fiber processing, baking coating, heat-resistant adhesive and the like.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The invention is not limited to the examples. The parts and% in the examples are by weight unless otherwise specified.

Reference Example 1 98 parts of ethyl acrylate, 2 parts of methacrylic acid and 0.5 part of sodium dodecylbenzene sulfonate were added to 35 parts of soft water and stirred to obtain a monomer emulsion. Separately, the inside of the reactor equipped with a thermometer, a stirrer, a reflux condenser, a supply pipe and a nitrogen introduction pipe was replaced with nitrogen gas, and then 0.3 parts of sodium dodecylbenzenesulfonate and 85 parts of soft water were charged. Then, the reactor is heated to 60 ° C., and 10 of the monomer emulsions are heated.
%, And after stirring for 10 minutes, 10 parts of a 5% aqueous solution of ammonium persulfate was added and the reaction was started with stirring. After 1 hour from the start of the reaction, 6 parts of an aqueous solution of 5% ammonium persulfate was added, and then the remaining monomer emulsion was added to
Add to reactor over time. After the addition of the monomer emulsion was completed, the reaction was further continued for 2 hours, finally cooled to 20 ° C., and the pressure was reduced to remove the residual monomer to obtain a polymer latex A. Latex A has a solid content of 41.6%,
The pH was 5.5.

Reference Example 2 10 parts of seed latex (methyl methacrylate polymer) (solid content), 46 parts of 1,3-butadiene, 40 parts of styrene, 2 parts of methacrylic acid, 1 part of acrylic acid, 1 part of acrylamide in an autoclave. 0.5 parts of sodium dodecylbenzene sulfonate and 140 parts of soft water were charged and stirred for 10 minutes, then the reactor was heated to 50 ° C. and 6 parts of a 5% potassium persulfate aqueous solution was added to start the reaction. Eight hours after the start of the reaction, the mixture was cooled to 20 ° C. and the pressure was reduced to remove the residual monomer to obtain a polymer latex B. Latex B had a solid content concentration of 42.3% and a pH of 5.3.

Example 1 54 parts of soft water, 35.3 parts of toluene, 2 parts of sodium dodecylbenzene sulfonate, 2 parts of 1-butanol and 5-ethyl-3-phenyl-1-aza-4,6-as a cross-linking agent.
Dioxabicyclo [3,3,0] octane (6.7 parts) was mixed and stirred using a T-type ultrasonic stirrer to obtain a bicyclic amide acetal dispersion liquid. Next, polymer latex A
6 parts of the above dispersion liquid was added to 18.4 parts (in terms of solid content) and stirred to obtain a polymer composition of the present invention. Then, the polymer composition was cast on a glass plate with a frame and left in an atmosphere of 20 ° C. for 48 hours, and then left in an oven having an internal temperature of 130 ° C. for 20 minutes to give a film as a crosslinked product of the present invention. Obtained. No formalin was generated when the film was obtained.

This film was evaluated by the following methods. The results are shown in Table 1. (Evaluation method) Solvent dissolution resistance test The film was put in a 100-mesh wire net and this was put at 20 ° C.
After immersing in the tetrahydrofuran for 24 hours, the constant amount of the solid content remaining in the wire net was determined and expressed as a percentage with respect to the constant weight of the film initially put in the wire net. Tensile test A film having a thickness of 0.4 mm was punched with a standard No. 2 dumbbell-type punching blade to obtain a test piece, and a distance between chucks was 5 cm using a constant-speed tension type tensile tester.
The measurement was performed under the conditions of a pulling speed of 300 mm / min.

Example 2 The procedure of Example 1 was repeated except that the amount of the bicyclic amide acetal dispersion liquid was changed to 3 parts to obtain a polymer composition of the present invention and a crosslinked product of the present invention. I got a film of. No formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 1.
It was shown to.

Example 3 In Example 1, 5-methyl-3-phenyl-1-aza-4,6-dioxabicyclo [3,3,0] octane was replaced by 5-methyl-3-phenyl as a cross-linking agent. -1-
A polymer composition of the present invention and a film as a crosslinked product of the present invention were obtained in the same manner as in Example 1 except that aza-4,6-dioxabicyclo [3,3,0] octane was used. No formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 1.

Example 4 In Example 1, 1,4-bis [as a cross-linking agent was used instead of 5-ethyl-3-phenyl-1-aza-4,6-dioxabicyclo [3,3,0] octane. 5-ethyl-1
-Aza-4,6-dioxabicyclo [3,3,0] octan-3-ylmethyloxy] butane was used in the same manner as in Example 1 except that the polymer composition of the present invention and the crosslinking of the present invention were used. I got a body film. No formalin was generated when the film was obtained. About this film Example 1
The evaluation was performed in the same manner as above and the results are shown in Table 1.

Example 5 In the same manner as in Example 1 except that the polymer latex B was used in place of the polymer latex A in Example 1,
A film was obtained as the polymer composition of the present invention and the crosslinked product of the present invention. No formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 1.

Example 6 96 parts of ethyl acrylate, 2 parts of methacrylic acid, 2 parts of 5-ethyl-3-phenyl-1-aza-4,6-dioxabicyclo [3,3,0] octane, dodecylbenzenesulfone 2.4 parts of acid soda, 0.07 part of paramenthane hydroperoxide and 30 parts of soft water were mixed and stirred to obtain an emulsion of a monomer and a bicyclic amide acetal. Separately, sodium-formaldehyde-sulfoxylate 0.
04 parts, ethylenediaminetetraacetic acid tetrasodium salt 0.0
12 parts and 0.02 part of sodium iron ethylenediaminetetraacetate dihydrate were dissolved in soft water to obtain a 2% aqueous solution L. Further, 0.32 part of sodium-formaldehyde-sulfoxylate and 0.02 part of frost iron were dissolved in soft water to obtain a 0.34% aqueous solution M. Next, after replacing the inside of the reactor equipped with a thermometer, a stirrer, a reflux condenser, a supply pipe and a nitrogen introduction pipe with nitrogen gas, 2.4 parts of sodium dodecylbenzenesulfonate and 260 parts of soft water were charged. Then, the reactor was cooled to 10 ° C., 10% of the emulsion was added, stirred for 10 minutes, and then 0.07 part of paramenthane hydroperoxide and 7 parts of aqueous solution L were added and stirred. The reaction was started. Simultaneously with the start of the reaction, 70 parts of the aqueous solution M was added over 6 hours. Separately, 30 minutes after the start of addition of the aqueous solution M, the remaining emulsion was added to the reactor over 5 hours. After the addition of the emulsion and the aqueous solution M, the reaction is further continued for 1 hour, and finally, the temperature is raised to room temperature and the pressure is reduced to remove the residual monomer to obtain a polymer composition of the present invention and a crosslinked product of the present invention. I got a film of. No formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 1.

[0037]

[Table 1]

Comparative Example 1 A polymer composition and a film were obtained in the same manner as in Example 1, except that the bicyclic amide acetal dispersion was not used. No formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 2.

Comparative Example 2 A polymer composition and a crosslinked product were prepared in the same manner as in Example 1 except that 0.4 part of hexamethoxymethylmelamine was used in place of the bicyclic amide acetal dispersion. I got a film of. Formalin was generated when the film was obtained. This film was evaluated in the same manner as in Example 1 and the results are shown in Table 2.

[0040]

[Table 2]

From the above, the cross-linking agent of the present invention comprising a bicyclic amide acetal can cross-link a polymer having an active hydrogen-containing functional group without generating formalin, and thus the cross-linked product (film) of the present invention. It can be seen that is excellent in solvent solubility and tensile strength as in the case of using the conventional crosslinking agent.

Claims (4)

[Claims] 1. A cross-linking agent comprising a bicyclic amide acetal. 2. A polymer composition containing the cross-linking agent according to claim 1 and a polymer having an active hydrogen-containing functional group. 3. A method for crosslinking a polymer having an active hydrogen-containing functional group, which comprises using the crosslinking agent according to claim 1. 4. A crosslinked product of a polymer having an active hydrogen-containing functional group, which is obtained by crosslinking with the crosslinking agent according to claim 1.