JPH055871B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an adhesive composition for fishing nets. [Prior Art] Conventionally, there is an adhesive composition in which nylon is dissolved in a mixture of phenol and an alcohol having 1 to 5 carbon atoms, formaldehyde is added, and the mixture is heated and condensed (for example, Japanese Patent Publication No. 5280/1983). [Problems to be Solved by the Invention] However, this net has poor weather resistance, and the texture of the adhesive-treated fishing net becomes too hard, causing the adhesive to fall off due to friction. [Means for Solving the Problems] The present inventors have conducted intensive studies on adhesive compositions for fishing nets that have excellent weather resistance, less adhesive shedding, a long pot life, and excellent workability and curing properties. As a result, we have arrived at the present invention. That is, the present invention is an adhesive composition for fishing nets containing an isophorone diisocyanate prepolymer (A) blocked with an oxime blocking agent and a polyether polyamine (B). The isophorone diisocyanate-based prepolymer can be obtained by reacting isophorone diisocyanate with a polyol in an excess of isocyanate. As the polyol, a high molecular polyol and/or a low molecular polyol can be used. Examples of polyether polyols include compounds having a structure in which an alkylene oxide is added to a polyfunctional compound containing an active hydrogen atom, such as a polyhydric alcohol, a polyhydric phenol, or a polycarboxylic acid. The above polyhydric alcohols include ethylene glycol,
Divalent alcohols such as propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and trivalent or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. Alcohol, etc. Polyhydric phenols include polyhydric phenols such as pyrogallol and hydroquinone, as well as bisphenols such as bisphenol A; condensates of phenol and formaldehyde (novolac), such as the polyhydric phenols described in U.S. Pat. No. 3,265,641; Examples include phenols. Also, examples of aminos include ammonia; alkanolamines such as mono-, di-, and tri-ethanolamine, isopropanolamine, and aminoethylethanolamine; C ₁
~ _C20 alkylamines; _C2 - _C6 alkyl diamines, such as ethylene diamine, propylene diamine, hexamethylene diamine, polyalkylene polyamines, aliphatic amines such as ethylene triamine, triethylene tetramine; aniline, phenylene diamine, diamino Toluene, xylylene diamine, methylene dianiline, diphenyl ether diamine, and other aromatic amines; alicyclic amines such as isophorone diamine, cyclohexylene diamine; aminoethyl piperazine and others described in Japanese Patent Publication No. 1983-21044 Examples include heterocyclic aminos. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and timer acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid. Two or more of these active hydrogen atom-containing compounds may be used in combination. Among these, polyhydric alcohols are preferred. The alkylene oxide to be added to the active hydrogen atom-containing compound is an alkylene oxide having usually 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as EO, PO, 1,2-,2,
Examples include 3-, 1,3- and 1,4-butylene oxide. Alkylene oxides may be used alone or in combination of two or more, and in the latter case, block addition or random addition may be used. Among these alkylene oxides, preferred are PO,
EO and 1,4-butylene oxide (tetrahydrofuran). Specific examples of polyether polyols include polypropylene glycol and polytetramethylene glycol. Examples of polyester polyols include condensed polyester polyols obtained by reacting low-molecular polyols (such as the dihydric alcohols, trimethylolpropane, and glycerin) with dicarboxylic acids (such as the polycarboxylic acids) and lactones (such as ε-caprolactone). Examples include polyester polyols obtained by ring-opening polymerization of ). Examples of polycarbonate polyols include the above-mentioned di- and trihydric alcohols and carbonic acid diesters (dimethyl carbonate, diethyl carbonate, etc.)
Here are some things you can get more from. As the acrylic polyol, hydroxyl group-containing vinyl polymer (acrylic polyol), for example,
No. 58-57413 and Japanese Unexamined Patent Publication No. 58-57414. Among these, polyester polyols are preferred, and polycaprolactone polyols are particularly preferred. The molecular weight of high molecular weight polyols is usually 500 to 5000,
Preferably it is 800-3000. The number of functional groups is usually 2
~3. Examples of the low-molecular polyol include the polyhydric alcohols mentioned above as raw materials for polyether polyols and low-mole alkylene oxide adducts of the above-mentioned active hydrogen atom-containing compounds. In addition to the polyol, other low-molecular active hydrogen atom-containing compounds (for example, the alkanolamines and polyamines mentioned above as raw materials for the polyether polyol) can be used in combination, if necessary. Among these, preferred are trimethylolpropane and alkanolamine. The amount of polymeric polyol (vs. polyol) is usually
50-100% by weight, preferably 80-95% by weight.
The amount of low molecular weight polyol (relative to polyol) is usually 0.
-50% by weight, preferably 5-20% by weight. The isophorone diisocyanate in the present invention includes polymerized polyisocyanates such as isophorone diisocyanate and dimers and trimers thereof;
Carbodiimide modified products and Biuretz compounds can also be used. Further, if necessary, some other organic polyisocyanates can be used in combination. Examples of organic polyisocyanates include aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbon in the NCO group), cycloaliphatic polyisocyanates having 4 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 12 carbon atoms, carbon Six to twenty aromatic polyisocyanates and modified products of these polyisocyanates (modified products containing carbodiimide groups, uretdione groups, uretimine groups, urea groups, Biuret groups, and/or isocyanurate groups, etc.) can be used. As such polyisocyanate,
Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,
6,11-undecane triisocyanate, 2,
2,4-trimethylhexane diisocyanate,
Lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; dicyclohexylmethane diisocyanate (water) Added MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-ethyl isocyanate),
4-Cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, diethylbenzene isocyanate; water modified product of HDI; tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude) MDI), modified MDI (such as carbodiimide modified MDI), naphthylene diisocyanate; and mixtures of two or more of these. Preferred among these are aliphatic polyisocyanates and alicyclic polyisocyanates. The amount of these organic polyisocyanates (relative to isophorone diisocyanate) is usually 0 to 20% by weight,
Preferably it is 0 to 10% by weight. When obtaining NCO urethane prepolymer, isophorone diisocyanate and polyol are
MCO/OH equivalent ratio is usually 1.2 or more, preferably 1.5
~3. In the NCO urethane prepolymerization reaction,
The reaction temperature may be the same as the temperature normally employed in the urethane prepolymerization reaction in the industry, and is usually 20 to 150°C, preferably 50 to 100°C. This reaction may be carried out in the presence of a catalyst or solvent if necessary. As the catalyst and solvent, those described below can be used. The urethane prepolymer can be produced using production equipment commonly employed in the industry. The oxime blocking agents used in the present invention include acetoxime, methyl ethyl ketoxime, and cyclohexanoxime. Among these, methyl ethyl ketoxime is preferred. Further, if necessary, some other blocking agents may be used in combination. The blocking agents include lactams, active methylene compounds and phenols. Lactams include ε-caprolactam and δ-
Parerolactam, γ-butyrolactam and β-
Propiolactam can be given. Active methylene compounds include malonic acid diesters (such as diethyl malonate), acetylacetone, and acetoacetate esters (such as ethyl acetoacetate). Phenols include phenol, cresol, xylenol and resorcinol. Preferred among other blocking agents are lactams. The amount of these other blocking agents (relative to oxime blocking agents) is usually 0 to 20% by weight, preferably 0 to 10% by weight. When obtaining the isophorone diisocyanate prepolymer (A) blocked with an oxime blocking agent, the NCO/OH equivalent ratio of the blocking agent containing the NCO urethane prepolymer and the oxime blocking agent is usually 0.5 to 1, preferably 0.7 to 1. It is 0.9. The reaction between the NCO urethane prepolymer and a blocking agent, including an oxime-based blocking agent, is as described above.
It can be carried out in the same manner as described in the section of NCO urethane prepolymerization reaction. The polyether polyamine (B) used in the present invention includes, for example, polyamines derived from polyalkylene polyols such as polypropylene glycol or triol. Specifically, for example, the general formula [where n is 1 to about 100]. ]or (In the formula, x+y+z is about 3 to 50.) Examples include polyoxypropylene polyamines represented by the following formula. The polyoxyalkylene polyamine may be used as is, but it may be used as a ketone (aliphatic ketone, such as acetone, methyl ethyl ketone,
Methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, diisopropyl ketone,
It can also be used as a so-called ketimine or enamine by reacting with dibutyl ketone, diisobutyl ketone, etc.). Polyether polyamines also include ketimines or enamines. The molecular weight of the polyether polyamine (B) is preferably 150 to 3000, more preferably 200 to 1000.
It is. The number of functional groups of the polyether polyamine (B) is usually 2 to 4. Among (B), preferred is polyoxypropylene polyamine. Further, if necessary, a part of a low molecular weight polyol can be used in combination with the polyether polyamine. The low-molecular polyol is the same as the low-molecular polyol described in the section on polyols above. The amount of these low molecular weight polyols (based on polyoxyalkylene polyamine) is usually 0 to 20% by weight, preferably 0 to 10% by weight. In the adhesive composition of the present invention, the potential of (A)
The equivalence ratio of the NCO group and the active hydrogen-containing group (B) is:
Usually 0.8-1.5:1, preferably 0.9-1.2:
It is 1. (A) and (B) are usually mixed uniformly using a solvent before use. Examples of solvents include aromatic hydrocarbons (toluene, xylene, etc.), esters (ethyl acetate,
Methyl cellosolve acetate, etc.), ketone type (methyl ethyl ketone, methyl isobutyl ketone, etc.), amide type (dimethylformamide N-methylpyrrolidone, etc.), sulfoxide type (dimethyl sulfoxide, etc.), chlorine type (carbon tetrachloride, trichlorethylene, etc.), etc. These solvents may be used singly or in mixtures. Among these, preferred are aromatic hydrocarbon-based, ketone-based, and ester-based solvents alone or in combination. Further, a catalyst and an additive can be used if necessary. Any known catalyst can be used.
Specifically, metal salts of carboxylic acids, such as sodium acetate, lead octylate, zinc octylate, cobalt naphthenate, etc.; Alkoxides and phenoxides of alkali and alkaline earth metals, such as sodium methoxide, sodium phenoxide: tertiary Amines, such as triethylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, pyridine, etc.; Quaternary ammonium bases, such as tetraethylammonium hydroxy; Imidazoles, such as imidazole, 2-ethyl-4-methylimidazole, etc.; tin. and organic metal compounds such as lead and antimony, such as tetraphenyltin and tributylantimony oxide. Preferred among these are organic compounds of metals such as tin and lead, tertiary amines, and mixtures thereof. The amount of catalyst used (pair (A) + (B)) is usually 0.001
~5% by weight. Preferably it is 0.01 to 1% by weight. Additives used in the present invention include antioxidants and/or ultraviolet absorbers. Known antioxidants and ultraviolet absorbers can be used. Specific examples of the antioxidant include hindered phenol compounds, hindered amine compounds, gallic acid esters, etc. Among these, preferred are hindered amine compounds. Examples of the ultraviolet absorber include benzotriazole type and benzophenone type, and among these, benzotriazole type is preferred. The amount of antioxidant and/or ultraviolet absorber used (vs. (A) + (B)) is usually 0.01 to 5% by weight,
Preferably it is 0.1 to 2% by weight. Other known additives such as colorants (pigments, dyes), plasticizers, inorganic fillers, etc. can also be used if necessary. The adhesive composition of the present invention can be applied to synthetic fiber fish nets. Synthetic fibers include nylon, vinylon, polyester, vinylidene chloride, and vinyl chloride. Fishing nets are classified into knotted nets, knotless nets, woven nets, and woven nets depending on the configuration of the mesh, and among these, the woven nets are preferred. The adhesive composition of the present invention can be applied to fishing nets by conventional treatment methods such as dipping, spraying, etc.
Preferred is the immersion method. After the adhesive composition is applied to the fishing net, it is baked and cured at a high temperature to adhesively fix the knots of the mesh. Baking temperature is usually 100-180℃, preferably 120℃
~160℃. Baking time is usually 10-120 minutes.
Preferably it is 20 to 60 minutes. [Examples] Hereinafter, the present invention will be further explained with reference to Examples.
The present invention is not limited to this. In the following, parts indicate parts by weight. Example 1 999 parts of isophorone diisocyanate, 2000 parts of polycaprolactone polyol (molecular weight = 2000, number of functional groups = 2) and 134 parts of trimethylolpropane
Blocked isocyanate (50% toluene solution) from 1 part (NCO/OH equivalent ratio = 1.8) of urethane prepolymer and 348 parts of methyl ethyl ketoxime (NCO/active hydrogen equivalent ratio of prepolymer = 1)
100 parts of polyoxypropylene polyamine (molecular weight = 400, number of functional groups = 3) and 7.6 parts (latent NCO/active hydrogen equivalent ratio = 1) were blended to obtain an adhesive composition. This composition was impregnated using a nylon mesh net, and then baked and cured at 140°C for 30 minutes. Example 2 A nylon gauze net was impregnated and cured by baking in the same manner as in Example 1 except that polyoxypropylene glycol (molecular weight = 2000, number of functional groups = 2) was used instead of polycaprolactone polyol. Comparative Example 1 An adhesive composition was obtained by heat condensation reaction from 100 parts of phenol, 30 parts of nylon-6, 70 parts of methanol, 30 parts of urea, and 160 parts of formaldehyde (37% aqueous solution). For this composition, Example 1
In the same manner as above, a nylon mesh net was impregnated and baked to harden. Test Example 1 The nylon nets obtained in Examples 1 and 2 and Comparative Example 1 were tested for weather resistance and kneading resistance. The test results are shown in Table-1.

[Table] [Effects of the Invention] The adhesive composition of the present invention has the following effects. (1) Excellent weather resistance. (2) Excellent kneading resistance. (3) Long pot life and excellent curing properties. (4) Excellent adhesion. Therefore, the adhesive composition of the present invention is useful as an adhesive for fishing nets.

Claims (1)

[Claims] 1. An adhesive composition for fishing nets containing an isophorone diisocyanate prepolymer (A) blocked with an oxime blocking agent and a polyether polyamine (B).