JPS6351474B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesion improver for organic polymer materials, and more specifically, it is capable of modifying various surfaces of natural or synthetic organic polymer materials to improve adhesion, and enhancing the adhesion of adhesive layers. This invention relates to an adhesion improver made of a heat-reactive water-soluble urethane resin. Conventionally, polyisocyanate compounds having free isocyanate groups or urethane prepolymers have been used to bond organic polymeric materials, especially synthetic polymeric materials that are generally difficult to adhere to, such as polyester, nylon, polyvinyl chloride, and polypropylene. Although these free isocyanate groups have been used, they are undesirable because they have disadvantages such as being susceptible to reactions and deterioration due to moisture, and containing large amounts of harmful and dangerous organic solvents. Therefore,
As other methods, various proposals have been made to use aqueous dispersions of blocked polyisocyanates, but these differ only in the means of making them into aqueous systems, and the resulting aqueous dispersions are Because the solution stability is poor and there is a tendency for precipitation and separation within a short period of time, reproducible adhesion cannot be obtained in many cases. In other words, many blocked isocyanate compounds generally have strong crystallinity, and by ball milling with a surfactant or by adding a salt-forming compound that is reactive with isocyanate groups, it is possible to remove ionic groups, such as ethylene oxide, etc. Even by self-emulsification by introducing nonionic groups by addition, it is difficult to obtain a stable aqueous dispersion, and even if it were possible to maintain the stability of the aqueous dispersion, it may be detrimental to adhesion. surfactant or
At present, it contains a large amount of ionic groups and nonionic groups, and has not yet reached a fully satisfactory level of adhesion. Note that blocked isocyanate compounds, like other water-based adhesives such as epoxy compounds, ethylene urea compounds, and isocyanurate compounds, generally only provide hard adhesion, and it is difficult to obtain a flexible and strong adhesive layer. It was hot. The present invention was developed as a result of extensive research into an adhesive improver for organic polymer materials that can solve the problems of conventional water-based adhesives and provide excellent stability and flexible adhesion. It is something. The adhesion improver of the present invention is characterized by comprising a heat-reactive water-soluble polyurethane resin represented by the following general formula. However, A: organic polyisocyanate residue having a functional number of 3 to 5. Y: Blocking agent residue that releases isocyanate groups by heat treatment. Z: a residue of a compound containing at least one active hydrogen atom and at least one anion-forming group in the molecule. X: a residue of a compound selected from the group consisting of (a) to (g) below, having 2 to 4 active hydrogen atoms and an average molecular weight of 5000 or less, (a) having 2 to 4 hydroxyl groups; (b) polyhydric amines having 2 to 4 primary and/or secondary amino groups; (c) 2 to 4 primary and/or secondary amino groups; (d) Polyester polyols having 2 to 4 hydroxyl groups; (e) Polybutadiene polyols having 2 to 4 hydroxyl groups and copolymers thereof with other vinyl monomers. , (f) polychloroprene polyols having 2 to 4 hydroxyl groups and copolymers thereof with other vinyl monomers, (g) polyether polyols having 2 to 4 hydroxyl groups, (i ) _C2 to _C4 alkylene oxide polyadducts of polyhydric amines, polyhydric phenols and amino alcohols; (ii) _C2 to _C4 polyhydric alcohols of C3 _or more;
(iii) _C2 - _C4 alkylene oxide copolymer, (iv) _C3 - _C4 alkylene oxide polymer. n: an integer from 2 to 4. l+m: An integer from 2 to 4, m≧0.25. That is, the adhesion improver represented by the above formula (1) of the present invention is a compound X-(H) _o having an average molecular weight of 5000 or less and having 2 to 4 active hydrogen atoms in the molecule [However,
n=2-4] and organic polyisocyanate A-(NCO) with a functional number of 3-5 _L+n+1 [However, l+m+1=
A part of the free isocyanate group [-(NCO _{) L+n} ] _o of the urethane prepolymer X-[NHCO-A-(NCO) _L+n ] o obtained by the reaction with [3-5] (NCO) _Lxo is blocked with blocking agent Y--H to form -(NHCOY) _Lxo , and the remaining isocyanate group - ( _NCO ) By reacting with the compound Z-H which has one
(NHCOZ) _NXO . Next, to illustrate typical components of the adhesiveness improver of the present invention, polyisocyanate A-(NCO) _L+n+1 constituting A includes, for example, tris-(isocyanatehexyl)- Retto polyisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, as well as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate,
Included are polyisocyanates obtained by reacting diisocyanates such as diphenylmethane diisocyanate with low molecular weight polyols such as trimethylolpropane, trimers of hexamethylene diisocyanate or tolylene diisocyanate, and the like. Examples of the compound X-(H) _o having 2 to 4 active hydrogen atoms constituting X include (a) ethylene glycol, butylene glycol,
Polyhydric alcohols such as propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, trishydroxyethyl isocyanate, (b) ethylenediamine, hexamethylenediamine, phenylenediamine, distyrenetriamine, and these (c) Polyvalent amines such as polyamide polyamines which are polycondensation products with adipic acid, maleic acid, phthalic acid, dimer acid, etc.; (c) Amino alcohols such as ethanolamine, diethanolamine, triethanolamine and propanolamine; d) Polycarboxylic acids such as adipic acid, succinic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid and dimer acid, and ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, trimethylol. Polyester polyols such as polycondensation products with polyhydric alcohols such as propane, glycerin trishydroxyethyl isocyanurate, or lactone polyester polyols obtained by ring-opening polymerization of caprolactone; (e) polybutadiene polyols such as polybutadiene glycol, and styrene and polycondensation products thereof; , copolymers with other vinyl monomers such as acrylonitrile, (f) polychloroprene polyols such as polychloroprene glycol and copolymers thereof with other vinyl monomers such as styrene, acrylonitrile, (g) (i) ethylenediamine, hexa Polyvalent amines such as methylenediamine and diethylenetriamine, polyvalent phenols such as resorcinol, 4,4'-dihydroxydiphenyl-2,2'-propane, and 4,4'-dihydroxydiphenylsulfone, and monoethanolamine and diethanolamine. , a polyether obtained by polyaddition of at least one alkylene oxide having 2 to 4 carbon atoms in the molecule, such as ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide, to an amino alcohol such as triethanolamine. polyols, (ii) polyhydric alcohols having 3 or more carbon atoms in the molecule, such as propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, glycerin, trishydroxyethyl isocyanurate, and pentaerythritol; (iii) polyether polyols in which at least one alkylene oxide having 2 to 4 carbon atoms is polyadded to the molecule; (iii) polyether polyols containing at least one alkylene oxide having 2 to 4 carbon atoms in the molecule; Examples include polymerized polyether glycols, (iv) homopolymers of alkylene oxides having 3 to 4 carbon atoms in the molecule, such as polypropylene glycol, polybutylene glycol, and polytetramethylene glycol. In addition, as the X component, polythioether, polyacetal, polyesteramide, acrylic polyol, etc., which are used in general polyurethane production, can also be used. Further, as the blocking agent Y-H constituting Y, for example, phenols such as phenol, chlorophenol, and cresol, p-sec-butylphenol, p-tert-butylphenol, p-
Alkylphenols such as sec-amylphenol, p-octylphenol, p-nonylphenol, secondary or tertiary alcohols such as isopropyl alcohol, tert-butyl alcohol,
Oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, lactams such as ε-caprolactam and δ-valerolactam, active methylene compounds such as malonic acid dialkyl ester, acetylacetone, and acetoacetic acid alkyl ester, 3-hydroxypyridine, 8-hydroxy Examples include basic nitrogen compounds such as Norin, and bisulfites. Furthermore, examples of the compound Z-H constituting Z include aminosulfonic acids such as taurine, N-methyltaurine, N-butyltaurine, and sulfanilic acid, and aminocarboxylic acids such as glycine and alanine. Compound X(-H) _o containing 2 to 4 active hydrogen atoms in the molecule and having an average molecular weight of 5000 or less, and organic polyisocyanate A(-NCO) _l+n+1 having a functional number (l+m+1) of 3 to 5. The reaction with
Preferably, it is carried out at 60 to 120°C for several minutes to several hours, but in this case, the molar ratio of isocyanate group/active hydrogen atom is independent of the type of X(-H) _o , molecular weight, and functional number (n). is defined solely by the functionality (3 to 5) of the organic polyisocyanate used. That is, in the case of an organic polyisocyanate having a functional number of 3, the molar ratio of isocyanate group/active hydrogen atom is 3, and in the case of a functional number of 5, it is 5,
As a result, the urethane prepolymer [(NCO _l+n+1 -A-NHCO]- _o If the number of functionalities is smaller than that of the organic polyisocyanate used for the purpose, not only will the urethane prepolymer which is the backbone of the above general formula not be formed, but a chain elongation reaction will occur, reducing the effective isocyanate groups, and in some cases, the gel On the other hand, if the functional number is greater than the organic polyisocyanate functionality, the chain extension reaction will not occur and there is no concern about gelation, but a portion of the organic polyisocyanate that will not be prepolymerized will remain. It does not satisfy the general formula of the present invention and does not provide the stable water-soluble polyurethane material that is its characteristic.Next, the blocking reaction of free isocyanate with YH is carried out in the presence of an appropriate inert solvent or in the presence of an inert solvent. The reaction is carried out at a temperature of 50-90°C, optionally using a basic catalyst such as triethylamine or an organometallic catalyst such as dibutyltin dilaurate. The reaction of the partially blocked urethane prepolymer with a compound containing a hydrogen atom and at least one anion-forming group can be carried out using a suitable compound capable of previously converting the anion-forming group into a salt form, such as ethylamine, triethylamine, Primary, secondary and tertiary amines such as dimethylamine and pyridine;
organic bases such as alkoxylated amines such as ethanolamine, diethanolamine, triethanolamine, and ammonia and hydroxides of one metal such as potassium hydroxide, sodium hydroxide, sodium bicarbonate, potassium carbonate, It is preferable to convert it into a salt-like group using inorganic bases such as carbonates and oxides, and then add it to the reaction system as an aqueous solution or a solution in an organic solvent. The reaction system is usually at a temperature of 20 to 60°C, and the two are mixed and kept at the same temperature until the addition reaction is completed. When the reaction is completed, the adhesion improver is diluted with water to obtain the present adhesion improver, which is a transparent to slightly cloudy stable heat-reactive water-soluble urethane resin with a solid content of 10 to 50%. Regarding l and m in general formula (1), the functional number of organic polyisocyanate A(-NCO) _l+n+1 is 3 to
5, so l+m is 2, which is 1 less than this.
~4, and furthermore, in order to ensure the water solubility of the polyurethane resin, at least one (ZCONH) group is required in the molecule (m×n≧1), so m≧1/
Since n is 2 to 4, m must be at least 0.25 or more. The adhesion improver of the present invention, that is, the heat-reactive water-soluble urethane resin represented by formula (1), provides very good and stable water solubility compared to conventional blocked isocyanate compounds. The following can be considered. That is, blocks of relatively low molecular weight polyisocyanate compounds are hydrophobic and highly crystalline, and when simply emulsified, stable dispersibility cannot be obtained unless a large amount of emulsifier is used. Even in the case of self-emulsification by introducing ionic groups, it is essential to introduce a considerably large amount of ionic groups. Therefore, conventional methods that require increasing the number of emulsifiers or ionic groups that are harmful or useless to adhesion to ensure solution stability lead to extremely poor adhesion performance; on the other hand, if adhesive performance is to be maintained, The reality was that only unstable products could be obtained.
In contrast, the heat-reactive water-soluble urethane resin of the present invention combines a compound with an average molecular weight of 5,000 or less containing 2 to 4 active hydrogen atoms in the molecule and an organic polyisocyanate with a functional number of 3 to 5 to form an isocyanate group. /
It is characterized in that it uses a urethane prepolymer of the general formula [(NCO) _l+n -A-NHCO]- _o X obtained by urethanization with an active hydrogen atom molar ratio in the range of 3 to 5. Compared to the above-mentioned polyisocyanate compounds, this urethane prepolymer, which forms the backbone of the present invention,
It has a structure in which the crystallinity of the polyisocyanate compound is moderately reduced, and the number of isocyanate functionalities per molecule is increased, so the uniformity of the addition of ionic groups per molecule during the ion-forming group introduction process is improved. As a result, it is thought that stable water solubility can be obtained. This can be seen as a clear difference in the ratio of introduced blocked isocyanate groups and ionic groups that can provide stable water solubility to the isocyanate groups contained in the polyisocyanate compound and the present urethane prepolymer. Next, as mentioned above, the provision of a flexible adhesive layer, which is another feature of the adhesion improver of the present invention, is due to the structure of the urethane prepolymer forming its skeleton. That is, this adhesion improver is a partially blocked urethane prepolymer into which an active hydrogen-containing compound with a molecular weight of 5,000 or less is introduced as a soft segment that moderately reduces the crystal structure of polyisocyanate, and the molecular weight can be increased by heat treatment. This forms a polyurethane elastomer. The adhesion improver of the present invention includes cellulose, wool,
Adhesion of the same or different types of synthetic and semi-synthetic organic polymer compounds such as silk, leather, and rubber, synthetic resins, synthetic fibers, synthetic rubber, cellulose derivatives, and rubber derivatives, or adhesion of these to metals, glass, and other materials. All of them are effective for adhesion to ceramic materials, etc., but especially for improving the adhesion of polyester and rubber, nylon and rubber, nylon and polyvinyl chloride, polyester and polyvinyl chloride, polyvinyl chloride and cotton, polypropylene and paper, etc. Significant effects were observed. The polyester, nylon, etc. mentioned here include fibers, cords, woven fabrics, non-woven fabrics, knitted fabrics, sheets, felts, films, etc. As for rubber, both ordinary natural and synthetic rubbers are effective. Polyvinyl chloride can also be used in any form, such as a film, sheet, or board, and may be either soft or hard. When adhering, for example, a flexible polyvinyl chloride sheet and polyester cloth using the adhesion improver of the present invention, the usual procedure is to apply or impregnate the polyester cloth with the adhesion improver as an aqueous liquid, and then A suitable method is to dry it at ~120°C, then laminate it with a soft polyvinyl chloride sheet and press-bond it at about 150~250°C. In addition, since the adhesion improver of the present invention has good compatibility with other water-based resins, it can be used in combination with other water-based resin adhesives, such as latexes such as polyepoxide compounds, ethylene urea compounds, SBR, NBR, etc.
It can also be added to melamine formalin resin, phenol formalin resin, urea formalin resin, resorcinol formalin resin, acrylic emulsion, urethane emulsion, starch, gelatin, carboxymethyl cellulose, polyvinyl alcohol, and the like. Furthermore, in this case, it is also possible to add a small amount of surfactant, if necessary.
It is also possible to add plasticizers, pigments, fillers, etc. Furthermore, a very unique use of the present adhesion improver is as an adhesion pretreatment agent. That is, for example, after immersing a nylon cloth sheet in the present adhesion improver solution, it is dried at 100 to 120°C for 5 to 10 minutes, and the present adhesion improver, which is a heat-reactive water-soluble urethane resin, is applied to the surface of the nylon cloth sheet. or,
Further, by heat treatment at 150 to 250°C, the surface is modified by forming a self-polymer layer of thermally dissociated isocyanate compounds. In this way, the nylon cloth sheet coated or surface-modified with the present adhesion improver can be extremely advantageously and easily subjected to heat bonding treatment with other water-based resins. The amount of this adhesion improver to be used is approximately 30% in solids based on the adherend material.
It is desirable to adjust it to about 0.5 to 10%. This adhesion improver can be used as an independent adhesive or
The mechanism for providing strong adhesion when used in combination with other resins or as an adhesion pretreatment agent is estimated as follows. That is, the present urethane prepolymer containing free isocyanate groups that are block-dissociated by heat treatment permeates and diffuses into the surface or inside of various organic materials and reacts with active hydrogen atoms contained in the organic polymer material, or It is thought that the adhesive reacts with active hydrogen atoms of other resins or self-polymerizes, thereby modifying the surface and significantly improving the cohesive force of the adhesive layer, thereby providing strong adhesion. This adhesion improver has better water solubility than conventional blocked isocyanate aqueous dispersions, and therefore has dramatically improved storage stability and compatibility with other water-based resins. It is an epoch-making product with high industrial value because it is flexible and can easily form strong bonds that are not found in conventional adhesives. Next, examples of the present invention will be shown, but the present invention is not limited thereto. Parts and % in the examples indicate parts by weight and % by weight unless otherwise specified. Production example of adhesion improver 1 Tolylene diisocyanate (2.4-, 2.6-isomer ratio 80:20) to 1 mol of trimethylolpropane
100 parts of triisocyanate with a free isocyanate group content of 19.2% obtained by reacting 3 moles with 6.9 parts of 1.4-butanediol (NCO/OH = 3), 85
Free isocyanate group content after reacting at ℃ for 60 minutes
106.9 parts of 11.9% urethane prepolymer were obtained.
Next, 28.6 parts of a solution of 7.2 parts of phenol dissolved in 21.4 parts of dioxane and 0.2 parts of triethylamine as a catalyst were added at 50°C, and gradually heated to 85°C.
The free isocyanate group content was 2.9.
% (based on urethane prepolymer) of a dioxane solution of partially blocked prepolymer was obtained. Next, 27.1 parts of a 40% taurine soda aqueous solution was added at 40°C, and after reacting at 40 to 50°C for 30 minutes, 462 parts of water was added to dilute it, resulting in a translucent, stable, homogeneous aqueous solution with a solid content of 20%. Obtained 624.8 copies. Production example 2 100 parts of tris-(isocyanatehexyl)-biuret polyisocyanate and 30 parts of dioxane
39.5 parts of a solution containing 5.6 parts of ethylenediamine (NCO/NH ₂ =3) and 22.8 parts of dioxane were gradually added to the mixed solution of 1 part at 25° C. under cooling. After the fever subsides, heat at 75℃ for 15 minutes.
Free isocyanate content 14.51%
179.5 parts of a urethane prepolymer dioxane solution was obtained. Next, 52 parts of a solution of 30.9 parts of ε-caprolactam dissolved in 21.1 parts of dioxane and 50 parts of tetramethylpropylenediamine as a catalyst were added.
C. and reacted for 90 minutes at 85.degree. C. to obtain 231.71 parts of a partially blocked prepolymer solution in dioxane with a free isocyanate content of 3.71%. Next, add 34.3 parts of 40% taurine soda aqueous solution at 40℃, and
After reacting for 30 minutes, 485.1 parts of water was added to dilute the mixture to obtain 751.1 parts of a homogeneous aqueous solution with a solid content of 20%. Production Example 3 50 parts of tris-(isocyanatehexyl)-biuret polyisocyanate (free isocyanate group content 23.5%) and 55 parts of 1.6-hexanediol-maleic anhydride ester glycol (hydroxyl value 95, acid value 1.6) ( NCO/OH=3) to 85
React for 60 minutes at °C, free isocyanate content
105 parts of 7.46% urethane prepolymer were obtained. Next, 34.1 parts of a solution of 13.1 parts of phenol dissolved in 21 parts of dioxane and triethylamine as a catalyst were added.
Add 0.21 part at 60℃, react at 85℃ for 60 minutes,
139.31 parts of a partially blocked prepolymer solution in dioxane with a free isocyanate content of 1.88% was obtained. Next, 17.3 parts of a 40% taurine soda aqueous solution was added at 40°C, and after reacting for 30 minutes at 40-50°C, it was diluted with 260 parts of water to form a viscous, transparent, uniform, and stable aqueous solution with a solid content of 30%.
Obtained 416.7 copies. Production Example 4 50 parts of tris-(isocyanatehexyl)-biuret polyisocyanate was reacted with 139.9 parts of polybutadiene glycol (average molecular weight 3000) (NCO/OH = 3) at 85°C for 60 minutes, resulting in a free isocyanate content of 4.12%. 189.9 parts of urethane prepolymer was obtained. Next, add 57 parts of dioxane to
A solution containing 12.2 parts of methyl ethyl ketoxime
69.2 parts were added at 60°C and reacted at 85°C for 30 minutes to obtain 259.1 parts of a partially blocked prepolymer solution in dioxane with a free isocyanate content of 1.01%. Next, add 14.8 parts of 30% glycine soda aqueous solution,
Add at 40℃ and react for 30 minutes at 40-50℃, then add water.
414.6 parts were added and diluted to obtain 688.5 parts of a viscous, translucent, homogeneous and stable aqueous solution with a solid content of 30%. Production Example 5 100 parts of tris-(isocyanatehexyl)-biuret polyisocyanate and 6.3 parts of pentaerythritol (NCO/OH=3) were heated at 85°C for 50
106.3 parts of a urethane prepolymer with a free isocyanate content of 14.72% was obtained. Next, 47.6 parts of a solution of 26.4 parts of methyl ethyl ketoxime dissolved in 21.2 parts of dioxane was added at 60°C, and
A solution of a partially blocked prepolymer with a free isocyanate group content of 2.71% in dioxane
Obtained 153.9 copies. Next, 25.2 parts of a 40% taurine soda aqueous solution was added at 40°C, and after reacting at 40 to 50°C for 30 minutes, 296.9 parts of water was added to dilute it to obtain 476 parts of a viscous and uniform aqueous solution with a solid content of 30%. Ta. Production Example 6 100 parts of polymethylene polyphenyl polyisocyanate (free isocyanate content 31.5%) and 24.4 parts of ethylene oxide 2 mole adduct of bisphenol A (hydroxyl value 35.4) (NCO/OH = 5),
React at 85℃ for 30 minutes to determine free isocyanate content.
124.4 parts of 20.26% urethane prepolymer were obtained.
Next, 134.2 parts of a solution of 72 parts of p-sec-butylphenol dissolved in 62.2 parts of dioxane and as a catalyst,
0.25 parts of triethylamine was added at 50°C, and the mixture was gradually heated and reacted at 85°C for 30 minutes to obtain 258.85 parts of a partially blocked prepolymer solution in dioxane having a free isocyanate content of 4.0%. Next, 43.6 parts of 40% taurine soda aqueous solution was added at 40℃, and
After reacting for 30 minutes, diluted by adding 552.9 parts of water.
855.4 parts of a translucent, stable, homogeneous aqueous solution with a solid content of 25% was obtained. Production example 7 Polymethylene polyphenyl polyisocyanate
100 parts of polyether triol (average molecular weight
500) (NCO/OH=5) were reacted at 85° C. for 30 minutes to obtain 125 parts of a urethane prepolymer with a free isocyanate content of 20.15%. Next, 118.5 parts of a solution of 81 parts of p-sec-butylphenol dissolved in 37.5 parts of dioxane and 0.25 parts of triethylamine as a catalyst were added at 50°C, and gradually heated.
Free isocyanate content was determined by reacting at 85℃ for 30 minutes.
243.75 parts of a 2.05% partially blocked prepolymer solution in dioxane was obtained. Next, 22.4 parts of a 40% taurine soda aqueous solution was added at 40°C, and after reacting at 40 to 50°C for 30 minutes, 808.85 parts of water was added to dilute the mixture to obtain 1.075 parts of a slightly cloudy homogeneous aqueous solution with a solid content of 20%. The following table shows the chemicals used in Production Examples 1 to 7 in relation to the formula (1) above.

【table】

[Table] Comparative Example 1 - Ball milled product of blocked polyisocyanate compound - Tolylene diisocyanate (2.4-, 2.6-isomer ratio 80:20) to 1 mole of trimethylolpropane
200 parts of a blocked polyisocyanate compound obtained by reacting 3 moles of triisocyanate with a free isocyanate group content of 19.2%, completely blocked with phenol, 10 parts of a sulfosuccinic acid dialkyl ester type anionic activator, and a polyoxyethylene nonyl phenol ether type non-active agent. Ionic activator (HLB12)
2 parts and 394 parts of water were processed in a ball mill for 24 hours,
606 parts of an aqueous dispersion with a solid content of 35% was obtained. Separation and precipitation of a blocked polyisocyanate compound was observed in this product after being left for about one day. Comparative Example 2 - Self-emulsified product of partially blocked polyisocyanate compound - Polymethylene polyphenyl isocyanate 100
134.4 parts of a solution of 84.4 parts of p-sec-butylphenol dissolved in 50 parts of dioxane and 0.2 parts of triethylamine as a catalyst were added to the mixture at 85°C.
A solution of partially blocked polyisocyanate in dioxane, reacted for 30 minutes and has a free isocyanate content of 7.81%.
Obtained 234.6 copies. Next, 68.4 parts of 40% taurine soda aqueous solution was added at 40°C, and after reacting at 40 to 50°C for 30 minutes,
494.2 parts of water was added and diluted to obtain 706 parts of a slightly cloudy aqueous dispersion with a solid content of 30%. This thing is about 2
After being left in the sun, a sandy precipitate was observed on the bottom. Comparative Example 3 - Emulsion of blocked urethane polymer with activator - 50 parts of tris-(hexyl isocyanate)-biuret polyisocyanate and 1.6-hexanediol-maleic anhydride ester glycol (hydroxyl value 95, acid value 1.6) 55 Department (NCO/OH=3)
were reacted at 85° C. for 60 minutes to obtain 105 parts of a urethane prepolymer with a free isocyanate content of 7.46%.
Next, 38.5 parts of a solution of 17.5 parts of phenol dissolved in 21 parts of dioxane and 0.21 parts of triethylamine as a catalyst were added at 60°C and reacted at 85°C for 60 minutes. I got the department. Next, sulfosuccinic acid dialkyl ester type anionic activator 10
1 part and 2 parts of a polyoxyethylene nonyl phenyl ether type nonionic surfactant were added thereto, and after uniformly dissolving, 292.6 parts of water was gradually added with stirring to obtain 448.3 parts of an emulsified dispersion with a solid content of 30%. Example 1 In the solutions obtained in Production Examples 1 to 7 and Comparative Examples 1 to 3,
A nylon cloth was soaked and squeezed to a solid content of about 2.0%, and then pre-dried at 100°C for 10 minutes. Next, this nylon cloth was placed on a soft vinyl chloride sheet and heat treated at 150° C. and 3 kg/cm ² for 3 minutes. The obtained sheet was cut to a width of 2.5 cm and a length of 10 cm, and the peel strength was measured using a tensile tester.
Table 1 shows the test results for peel strength, adhesive layer flexibility, and solution stability.

[Table] ×Poor As can be seen from Table 1, the adhesion improvers according to the present invention in Production Examples 1 to 7 are aqueous dispersions of conventionally known blocked isocyanates and blocked urethane prepolymers shown in Comparative Examples 1 to 3. Compared to liquids, it has superior adhesive properties such as high peel strength and provides a flexible adhesive layer, and has also significantly improved solution stability. Example 9 A nylon cord was immersed in the adhesive solutions of Production Examples 1 to 7 and Comparative Examples 1 to 3, and the solid content adhesion was approximately 2.0.
%, and then dried at 120°C for 3 minutes. Next, this dried cord is immersed in RFL (resorcinol-formalin-latex), and the RFL solid content is approximately 3.0%.
After adjusting it so that
Next, this processing code is embedded in natural rubber,
After heating at 150°C for 30 minutes, peel strength, pull-out strength and bending hardness were measured. In addition, for comparison, we measured the peeling, pull-out strength, and bending hardness when treated with only RFL (approximately 5% adhesion), and the test results are shown in Table 2 based on the index when this was used as a blank (100). Show the results.

[Table] From the above table, it can be seen that the adhesion improvers of Production Examples 1 to 7 clearly provide softer and stronger adhesion compared to the conventionally known ones shown in Comparative Examples 1 to 3. Example 10 Using the adhesive solutions of Production Examples 1 to 7 and Comparative Examples 1 to 3, a rubber sheet with a thickness of 1 mm and a hardness of 60, and a thickness of 0.5 mm.
polyethylene terephthalate film and thickness
0.04mm polypropylene film 5×10cm2 ^each
A 20% solids solution was uniformly applied to each 5 x 5 cm ² part, and the pieces were pasted together, pre-dried at 100°C for 10 minutes under a pressure of 2 kg/cm ² , and further dried at 150°C for 10 minutes. It was heat treated and bonded. Table 3 shows the results of measuring the adhesive peel strength of these products.

[Table] From the above table, it can be seen that all the adhesion improvers of the present invention provide better adhesion than the known ones shown in Comparative Examples 1 to 3. Example 11 Commercially available veneer board (thickness 4 mm) cut into 5 x 10 cm ² using Examples 1 to 7 and Comparative Examples 1 to 3 as adhesive
Apply a 20% solids solution evenly to a 5 x 5 cm ² area from the edge of the piece, and cut each piece into 5 x 15 cm ² pieces with a thickness of 0.5 mm.
It was laminated with a soft vinyl chloride sheet and pre-dried in an oven at 100°C for 10 minutes. Next, it was heat-treated in a hot press at 150°C for 5 minutes at a pressure of 2 kg/cm ² , and the 180°C peel strength of the resulting composite material was measured. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1. General formula (However, A: an organic polyisocyanate residue with a functional number of 3 to 5, Y: a blocking agent residue that releases an isocyanate group by heat treatment, Z: at least one active hydrogen atom and at least one anion in the molecule) Residue of a compound containing a formative group; , (a) polyhydric alcohols having 2 to 4 hydroxyl groups, (b) polyhydric amines having 2 to 4 primary and/or secondary amino groups, (c) 2 to 4 amino alcohols having a primary and/or secondary amino group and a hydroxyl group, (d) polyester polyols having 2 to 4 hydroxyl groups, (e) polybutadiene polyols having 2 to 4 hydroxyl groups, and Copolymers of these and other vinyl monomers, (f) Polychloroprene polyols having 2 to 4 hydroxyl groups and copolymers of these and other vinyl monomers, (g) Copolymers of 2 to 4 hydroxyl groups Polyether polyols having (i) C ₂ to _{C 4} alkylene oxide polyadducts of polyhydric amines, polyhydric phenols and amino alcohols, (ii) C ₂ of C ₃ or more polyhydric alcohols. ~ _C4
(iii) _C2 - _C4 alkylene oxide copolymer, (iv) _C3 - _C4 alkylene oxide polymer, n: an integer of 2-4, l+m: 2-4. An adhesion improver for organic polymer materials, characterized by comprising a heat-reactive water-soluble urethane resin represented by an integer m≧0.25).