JPH1030024A - Polycarbodiimide compound, its production, resin composition and treatment of article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain polycarbodiimide compound having such structure that the molecular chains are mutually bound in a branched fashion, capable of forming film adhesive or coating film on an article even under post-treatment condition at normal or relatively low temperatures, therefore useful as e.g. an adhesive. SOLUTION: This polycarbodiimide compound has such a structure that at least four molecular chains each bearing carbodiimide group are mutually bound in a branched fashion. It is preferably that this polycarbodiimide compound has an average molecular weight of 1,000-30,000 and is obtained by reaction between (A) an isocyanate compound bearing each at least one carbodiimide group and isocyanate group and (B) a polyol, polyamide and/or amino alcohol each bearing at least 4 OH groups, amino groups and/or imino groups in the molecule and, if needed, further reaction of (C) a monohydric alcohol or monoamine bearing one OH, amino or imino group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polycarbodiimide compound, a method for producing the same, a resin composition, and a method for bonding or coating an article. More specifically, the present invention relates to a polyfunctional reactive compound having a carbodiimide group as a reactive group useful as a crosslinking agent or a resin treatment agent for a reactive film-forming material, an adhesive, a method for producing the same, and a metal using the same. Adhesion and application to articles such as manufactured articles, synthetic resin articles, plastic films, wood products, woven fabrics, non-woven fabrics, paper, etc.
An object of the present invention is to provide a resin treatment agent for printing, impregnating or printing, and a method for bonding or coating the above article using the resin treatment agent.

[0002]

2. Description of the Related Art Conventionally, various resin treating agents have been used for resin processing or coloring of fibrous articles such as yarn, woven fabric, non-woven fabric, and paper. Metal products such as iron products and aluminum products, synthetic resin products such as polyethylene, polypropylene, polyvinyl chloride, ABS, polyester, and nylon; plastic films such as polyethylene, polypropylene, polyvinyl chloride, and polyester; and wood products. Various coating compositions have been used for painting, resin processing, surface coating and printing articles.

For example, an aqueous emulsion polymerization liquid such as an acrylic ester type, vinyl type, diene type or the like having a reactive group is used as a binder component as a pigment resin colorant for a woven fabric, and methylol as a crosslinking agent capable of reacting therewith. Group, alkylmethylol group, epoxy group, isocyanate group,
Ethyleneimine ring groups and the like have been used. Metal goods,
Synthetic resin articles, paints on wood products, etc., as gravure printing inks on plastic films, the binder components of which have reactive groups such as acrylic ester-based, vinyl-based, diene-based polymer solutions, aqueous polymer solutions, aqueous Emulsion polymerization liquids and the like have been used, and as a crosslinker capable of reacting therewith, similarly, methylol groups, alkylmethylol groups, epoxy groups, isocyanate groups, ethyleneimine ring groups and the like have been used.

[0004] However, in the field of woven fabrics, the material and shape of the fibers are diversified, and the fibers or woven fabrics may be deformed at a high post-treatment temperature. Is required to cause crosslinking. In addition, regarding hygiene, not only products such as resin-processed or colored woven fabrics but also sanitary and safe enough as treatment agents for fibrous articles such as pigment resin colorants. Has been requested.

In the field of paints, there are many paints which cannot be subjected to post-treatment such as heating. In such a case, a non-reactive high molecular weight polymer or an air-dry acrylic resin is used as a vehicle. Have been. Also, in the case of printing inks, the materials and shapes of plastic films are diversified, and some films may be deformed at high post-processing temperatures. Therefore, it is necessary to cause crosslinking at low or normal temperature. Have been. In addition, regarding hygiene, not only products such as coated or painted articles, but also coating compositions such as paints, coating agents, printing inks, etc., should be sufficiently hygienic and safe as well. Is required.

In response to such demands, attention has been paid to carbodiimide compounds which have been used as catalysts for amidation reactions between carboxyl groups and amino groups and for peptidation reactions of amino acids. It has been found that they can be used as a crosslinkable reactive group of a reactive polymer, and have higher hygiene and safety than other reactive groups. For example, a linear carbodiimide compound obtained by reacting a diisocyanate compound having a carbodiimide group obtained by condensing a diisocyanate compound with a monoisocyanate compound or a monoalcohol or dialcohol compound is used as a crosslinking agent for a polymer having a carboxyl group as a binder. It has been proposed.

[0007]

These carbodiimide compounds have been sufficiently evaluated in terms of hygiene and safety as compared with the above-mentioned reactive compounds used as conventional crosslinking agents. However, when looking at fibrous articles, for example, in woven fabrics, a wide variety of woven fabrics such as fiber materials, fiber cross-sectional shapes, weaving methods, etc. are widely used. Various restrictions such as conditions are added. In terms of robustness, even if the required robustness is obtained in a high-temperature baking treatment, in the case of a post-treatment at a low temperature or room temperature,
Especially dry and wet friction fastness against synthetic fiber woven fabric,
Defects such as insufficient fastness in washing and the like were exhibited.

[0008] Further, in the case of paints, coating agents and printing inks, regardless of the requirement for high robustness of the coated or printed material, the material to be coated is limited in terms of the material, or when the material is large or used in outdoor buildings. In many cases, the heating and crosslinking treatment cannot be performed due to factors such as the installation location. Under such circumstances, there is a demand for a cross-linking agent that provides sufficient robustness under processing conditions such as standing drying at normal temperature, air drying or low-temperature drying, but the carbodiimide compound as described above is a low-molecular compound. Or, it is a linear compound, and although it is a reactive compound, it has a defect that it does not show sufficient robustness to the above-mentioned post-treatment conditions at ordinary temperature or low temperature.

[0009] Under such circumstances, on the premise of hygiene and safety, and in the post-treatment at a low temperature or normal temperature, as well as a high-temperature baking treatment for a wide variety of woven fabrics to be used, etc. Also, there is a demand for the development of a treatment agent for fibrous articles such as an improved pigment resin colorant having sufficient fastness properties. Further, there is a demand for the development of an improved coating treatment agent for articles such as paints and printing inks having sufficient fastness even in post-treatment at room temperature.

The present inventors have conducted various studies in order to solve the above-mentioned defects of the conventional treating agent for fibrous articles and coating treating agents such as paints and printing inks. Using a forming reactive polymer, a treating agent using a multi-branched polyfunctional carbodiimide compound as a crosslinking agent can exhibit excellent properties even in post-treatment at low or normal temperature and can be obtained. The present inventors have found that the resin-treated or colored article is an excellent article which can satisfy various physical properties, and completed the present invention.

[0011]

The above object is achieved by the present invention described below. That is, the present invention provides a multi-branched polyfunctional polycarbodiimide compound characterized in that at least four or more molecular chains having a carbodiimide group are bonded in a branched form. An isocyanate compound (a) having at least one carbodiimide group and at least one isocyanate group and a polyol, polyamine and / or amino alcohol (b) having at least four hydroxyl groups, amino groups and / or imino groups in the molecule; And, if necessary, further reacted with a monoalcohol or a monoamine (c) having one hydroxyl group, amino group or imino group in the molecule, a multibranched polyfunctional polycarbodiimide compound, In a resin composition containing a production method, a reactive polymer and a crosslinking agent, a multi-branched polyfunctional polymer A resin composition using a crosslinkable polymer (B) having a reactive group having an easily transferable hydrogen capable of reacting a carbodiimide compound (A) with a reactive polymer as a reactive polymer and bonding an article using the same Or a coating treatment method.

The object of the present invention is to bond or coat an article by using a reactive polymer having a cross-linking property as a polymer film forming material, and forming a strong adhesive layer between the articles by forming a network with a cross-linking agent. Or to form a robust coated polymeric film on the article. In the linear low-molecular-weight carbodiimide compound as described above in which a cross-linking agent used for cross-linking the cross-linkable polymer has already been proposed, even if the number of functional groups per molecule is large, one of them is It is assumed that the cross-linking restricts the movement of the molecule. For that reason, the cross-linking reaction is often insufficient, and does not always contribute to the improvement of the density of the network of the polymer.

On the other hand, when a multi-branched polyfunctional carbodiimide compound, ie, a polyfunctional carbodiimide compound in which a polycarbodiimide molecular chain having many carbodiimide groups is radially branched, is used as a crosslinking agent. Branched molecular chains can move freely without being restricted to each other, and the number of carbodiimide groups in one molecule is extremely large.
Moreover, it is considered that the reaction of the carbodiimide group of one molecular chain occurs almost independently of the reaction of the carbodiimide group of the other molecular chain.

Therefore, only a part of the carbodiimide group in a certain molecular chain reacts with the reactive group of the crosslinkable polymer, the carbodiimide compound itself becomes the center of the network formation of the polymer and further forms the same molecule. A carbodiimide group cross-linking reaction occurs in the chain and in other molecular chains, and as the cross-linking reaction proceeds, the polymer is drastically converted into a cross-linked polymer having a high network density. Such a reaction mechanism has the effect of forming a robust coating film on the article.

[0015]

Next, the present invention will be described in more detail with reference to preferred embodiments. The multi-branched polyfunctional polycarbodiimide compound (A), which is used in the present invention and is a cross-linking agent which characterizes the present invention, is a form in which a polycarbodiimide molecular chain having many carbodiimide groups is radially branched as described above. A carbodiimide compound having one or more carbodiimide groups and 1
The isocyanate compound (a) having one or more isocyanate groups is reacted with a polyol, polyamine and / or amino alcohol (b) having four or more hydroxyl groups, amino groups and / or imino groups in the molecule, and In addition, a hydroxyl group, an amino group or an imino group may be added to the molecule according to
It is obtained by reacting a monoalcohol or a monoamine (c) having one or more of them.

Examples of the above-mentioned multi-branched polyfunctional polycarbodiimide compound (A) include the following. (1) Polyol having four or more hydroxyl groups, amino groups and / or imino groups in a molecule, isocyanate compound having one or more carbodiimide groups and one isocyanate group in polyamine and / or amino alcohol (b) ( A product obtained by reacting a-1) in an equal amount. (2) Polyol having four or more hydroxyl groups, amino groups and / or imino groups in the molecule, isocyanate compound having one or more carbodiimide groups and two or more isocyanate groups in polyamine and / or amino alcohol (b) One isocyanate group of (a-2) is reacted, and the remaining unreacted isocyanate group is further reacted with an equivalent amount of a monoalcohol or monoamine (c) having one hydroxyl group, amino group or imino group in the molecule. The product obtained by this.

(3) Polyol having 4 or more hydroxyl groups, amino groups and / or imino groups in the molecule, polyamine and / or amino alcohol (b) having one or more carbodiimide groups and one isocyanate group The isocyanate compound (a-1) is reacted, then the isocyanate compound (a-2) having one or more carbodiimide groups and two or more isocyanate groups is reacted, and the remaining unreacted isocyanate groups are further incorporated into the molecule. A product obtained by reacting a monoalcohol or monoamine (c) having one hydroxyl group, amino group or imino group. In the above, a polyol, polyamine and / or amino alcohol having two or three hydroxyl groups, amino groups and / or imino groups in the molecule may be added and used together to extend the molecular chain.

The isocyanate compound (a-1) having one or more carbodiimide groups and one isocyanate group used in the above can be prepared by subjecting a di- or polyisocyanate compound to, for example, 3-methyl-1
-Phenyl-3-phospholene-1-oxide, etc., in the presence of a carbodiimidization catalyst to react two isocyanate groups to form a carbodiimide group, and to leave one of the molecular terminal isocyanate groups. It is obtained by reacting the remaining isocyanate group with a monoisocyanate compound to form a carbodiimide group.
The isocyanate compound (a-2) having one or more carbodiimide groups and two or more isocyanate groups can be obtained by converting a di- or polyisocyanate compound into 3-methyl-1-phenyl-2-phospholene-1-oxide or the like. The reaction is carried out in the presence of a carbodiimidization catalyst to react two isocyanate groups to form a carbodiimide group, and to react so as to leave an isocyanate group at a molecular terminal.

The above isocyanate compounds a-1 and a
The number of carbodiimide groups in one molecule of -2 is not particularly limited, but is about 1 to 20, preferably about 2 to 10 because it is a raw material of a crosslinking agent. Examples of the di- or polyisocyanate compound used include conventionally known aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Specifically, for example, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, toluylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and polyisocyanate compounds obtained by dimerizing or trimerizing them with a biuret bond or an isocyanurate bond. Is mentioned.

Examples of the monoisocyanate compound include conventionally known aliphatic monoisocyanates, alicyclic monoisocyanates, aromatic monoisocyanates and α, β-ethylenically unsaturated isocyanates. Specific examples include hexyl isocyanate, phenyl isocyanate, toluene isocyanate, metalloyl isocyanate, metalloyloxyethyl isocyanate, m-isopropenyl-α, α′-dimethylbenzyl isocyanate.

Further, polyols, polyamines and / or amino alcohols having four or more hydroxyl groups, amino groups and / or imino groups in the molecule which is a factor for forming the hyperbranched type of the hyperbranched polycarbodiimide compound of the present invention. (B)
Aliphatic, alicyclic and aromatic polyols having four or more hydroxyl groups, amino groups and / or imino groups in the molecule, -polyamines, -amino alcohols; aliphatic, alicyclic and aromatic poly A hydroxy ester of a carboxylic acid; one or more polyols, polyamines or amino alcohols selected from hydrates of epoxy resins and the like.

Specifically, for example, polyglycerols such as diglycerin, tetraglycerin, hexaglycerin, decaglycerin, pentaerythritol, dipentaerythritol, sorbitan, sorbit and the like, and ethylene oxide adducts and propylene oxide adducts thereof; polyethylene Imines; ethylene oxide adducts and propylene oxide adducts of amines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and polyethyleneimine; ethylene oxide adducts and propylene oxide adducts of phenolic novolak resins; bisphenol A-epichlorohydrin addition Polyol obtained by reacting with water of polymer, reacting with water of trimethylolpropane polyglycidyl ether Polyol, a polyol obtained by reacting with water of polyglycerin polyglycidyl ether, a polyol obtained by reacting with water of sorbitan polyglycidyl ether; and 4 or more hydroxyl groups in a partially esterified product of these polyhydric alcohols Or one or more polyols, polyamines, or amino alcohols selected from alcohols and the like in which is left.

The monoalcohol or monoamine (c) having one hydroxyl group, amino group or imino group in the molecule to be further reacted, if necessary, includes aliphatic, alicyclic and aromatic monoalcohols or monoamines; And one or more monoalcohols or monoamines selected from alicyclic and aromatic polyalcohol monohydroxy polyethers, monohydroxy polyesters, monoalcohols having anionic or cationic groups, and the like.

Specifically, for example, aliphatic, alicyclic and aromatic monoalcohols having 1 to 18 carbon atoms, 2 to 4 carbon atoms
C1 to C18 aliphatic, alicyclic and aromatic hydrocarbon group monoether monoalcohols, C2 to C4 polyalkylene glycol C1 to C18 aliphatic and aliphatic Monoester monoalcohols of cyclic and aromatic monocarboxylic acids, having 1 to 1 carbon atoms
8 aliphatic, alicyclic and aromatic monoamines; anionic groups such as sulfone groups, sulfate groups and phosphate groups, or cationic groups such as tertiary amino groups, quaternary ammonium groups and pyridinium groups And one or more monoalcohols or monoamines selected from aliphatic, alicyclic and aromatic monoalcohols having 1 to 18 carbon atoms.

More specifically, sodium sulfonic acids such as hydroxymethanesulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid, monoethoxymonohydroxyethyl ester of sulfosuccinic acid, taurine, N-methyltaurine, sulfanilic acid, and metanilic acid And 2-hydroxyethyltrimethylammonium chloride such as salts and triethylamine salts. The average molecular weight of the multi-branched polyfunctional polycarbodiimide compound (A) is about 1,000 to 30,000, preferably about 2,000 to 20,000.

The crosslinkable polymer having a reactive group having a hydrogen which can be easily reacted with the multibranched polyfunctional polycarbodiimide compound (A) which is the crosslinker used as the reactive polymer. The combination (B) will be described. Examples of the reactive group having easily transferable hydrogen capable of reacting with the carbodiimide group include a carboxyl group, a hydroxyl group, an amino group, a thiol group, and the like.The crosslinkable polymer is selected from the above reactive group group. It contains one or more reactive groups. The content of the reactive group having hydrogen which is easily transferred and contained in the cross-linkable polymer varies depending on the type of the reactive group and is not determined unconditionally, but is about 0.1 to 10% by weight. , Preferably 0.5 to 5% by weight.

As the crosslinkable polymer, there are conventionally used, for example, various adhesives, paints, coating agents, printing inks, pigment resin printing agents, and fiber resin processing agents having the above-mentioned reactive groups. A crosslinkable polymer is used. Specifically, each of the above-mentioned reactive group polyacrylic ester-based, polyvinyl-based, polydiene-based addition polymerization-based polymer, polyurethane-based, polyurethane urea-based,
Examples include addition condensation polymers such as epoxy resins, condensation polymerization polymers such as alkyd resins, polyesters, and polyamides, rosin-modified resins, and derivatives of natural products such as cellulose derivatives.

Examples of the comonomer having a reactive group having a hydrogen which can be easily transferred and used for synthesizing the above-mentioned crosslinkable addition-polymerized polymer include acrylic acid, methacrylic acid, maleic acid, and the like. Unsaturated carboxylic acids such as fumaric acid and itaconic acid, and their hydroxyalkyl (C ₂ -C ₄ ) esters, polyoxyalkylene (C ₂ -C ₄ ) esters, glyceryl esters, etc.
Reactive monomers selected from the group consisting of allyl alcohol, allylamine, the above-mentioned monoesters and monoamides of unsaturated dicarboxylic acids, and the like.

Examples of the monomer to be copolymerized with the comonomer having such a reactive group include vinyl compounds such as vinyl chloride, vinyl acetate and styrene, alkylene compounds such as ethylene, butadiene and isoprene, and methyl acrylate. Acrylic esters such as (C ₁ ) to stearyl (C ₁₈ ) esters, cyclohexyl esters, and benzyl esters; and methyl (C ₁ ) to stearyl (C ₁₈ ) methacrylates
Examples include methacrylate monomers such as esters, cyclohexyl esters, and benzyl esters, and one kind or a mixture of two or more kinds is used.

The comonomer having a reactive group having a hydrogen which can be easily used for synthesizing the above-mentioned crosslinkable addition condensation polymer or condensation polymerization polymer includes trihydric anhydride. Menlitic acid, pyromellitic anhydride, half esters of these acid anhydrides and diols, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, lysine, arginine, aspartic acid, glutamic acid and the like. Further, a non-reactive polymer may be added to the above-mentioned components in combination with the dispersibility of the pigment and the affinity with the article to the extent that the physical properties of the coating film are not impaired.

In the treating agent for the article of the present invention, when used for coloring such as a pigment resin printing agent or a paint, the coloring agent used may be a conventionally known pigment, dye, colored polymer bead, or microencapsulated. Dyes and the like. Examples of pigments include organic pigments such as phthalocyanine, azo, azomethine azo, azomethine,
Anthraquinone, Perinone, Perylene, Indigo
It is a thioindigo-based, dioxazine-based, quinacridone-based, isoindolinone-isoindoline-based pigment, or a carbon black pigment, and examples of inorganic pigments include a titanium oxide pigment, an iron oxide-based pigment, a spinel-based fired pigment, and an extender pigment. When these pigments are used in aqueous or solvent-based paints or pigment resin printing agents, the pigments are previously prepared using a conventionally known surfactant or a water-soluble or solvent-soluble polymer dispersant as a dispersing aid. It is preferable to use a finely dispersed high density dispersion color.

The articles to be coated according to the present invention include metal articles, synthetic resin articles, plastic films, wood products, woven fabrics, non-woven fabrics, papers, and the like. Small articles such as
Large articles such as automobile bodies, metal articles such as buildings, polyethylene, polypropylene, polyvinyl chloride, AB
Synthetic resin articles such as S, polyester, nylon, etc., plastic films such as polyethylene, polypropylene, polyvinyl chloride, polyester, wooden products, plywood products,
Wood products such as wooden structures, fibrous articles such as yarn, woven fabric, non-woven fabric, and paper.

A method for bonding or coating an article, such as coating, printing, impregnating, printing or adhering, pressing, or adhering to such an article, will be described. In a resin composition for bonding or coating containing a reactive polymer and its crosslinking agent, the crosslinking agent is an isocyanate compound having at least one carbodiimide group and at least one or at least two isocyanate groups (a ) Is reacted with a polyol, polyamine and / or amino alcohol (b) having four or more hydroxyl groups, amino groups and / or imino groups in the molecule, and if necessary, further reacted with hydroxyl, amino or imino groups in the molecule. 1
A multi-branched polyfunctional polycarbodiimide compound (A), which is a reaction product obtained by reacting a monoalcohol or a monoamine (c) having two or more mono-alcohols or mono-amines (c), and having reactive hydrogen capable of reacting with the reactive polymer. A crosslinkable polymer (B) having a reactive group, and if necessary, a pigment, a dye,
An article characterized in that the article is coated, printed, impregnated or printed with a coating composition prepared by adding an antifoaming agent, a thickener, a leveling agent, and the like, and then subjected to room temperature or low temperature drying and / or heat treatment. Is a coating treatment method.

In particular, the present invention is to improve the cross-linking efficiency by making a polyfunctional polycarbodiimide compound capable of reacting even at a low temperature into a multi-branched type, and a post-treatment at room temperature to 100 ° C. or lower is desirable. It is effective for coating or bonding such as printing, resin processing, printing, painting and bonding of articles such as plastic film products, wood products, large parts, large structures and buildings.

[0035]

Next, the present invention will be described more specifically with reference to examples. It should be noted that “part” or “%” in the text is based on weight. Synthesis Example 1 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-1) Carbodiimidization was carried out in a condensation reactor equipped with a stirrer, a thermometer, a water content receiver equipped with a coiled condenser, a nitrogen gas inlet tube, and a dropping funnel. Polyhexamethylene carbodiimide diisocyanate having isocyanate groups at both ends obtained by condensation of four molecules of hexamethylene diisocyanate using 3-methyl-1-phenyl-3-phospholene-1-oxide as a catalyst (carbodiimide group in one molecule) Average number: about 2.8) 30% toluene solution 63
1.4 parts were added, 1.3 parts of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and the mixture was heated to 60 ° C.
Polyethylene glycol monomethyl ether (molecular weight:
468.5 parts of a 50% toluene solution of
The reaction was carried out dropwise over a period of minutes. Next, the temperature was gradually raised, and the reaction was continued at 100 ° C. for 3 hours. Next, decaglyceryl monolaurate (average number of hydroxyl groups in one molecule:
37.6 parts of a 50% toluene solution of about 11) was added dropwise at 100 ° C. over 60 minutes, and the reaction was further continued for 1 hour. The reaction was determined by infrared absorption spectroscopy by confirming the reduction of isocyanate groups and the formation of urethane groups.

Next, toluene is distilled off at 115 ° C. for 2 hours, and the pressure is further reduced to further distill off. 177 water at 50 ° C
0 parts were added to obtain an aqueous solution of a branched polycarbodiimide compound (solid content: 20%). Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-1. This compound has a molecular chain having 11 carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is about 30.

Synthesis Example 2 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-2) In the same manner as in Synthesis Example 1, a 30% toluene solution 574 of polyhexamethylene carbodiimide diisocyanate having isocyanate groups at both ends was placed in a condensation reactor. Then, 0.9 parts of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 233.6 parts of a 50% toluene solution of polypropylene glycol monobutyl ether (molecular weight: about 500) was added dropwise and reacted. Then, 35.0 parts of a 50% toluene solution of dipentaerythritol monolaurate (average number of hydroxyl groups in one molecule: about 5) was added dropwise, and the reaction was continued. Next, toluene was added to obtain a toluene solution of the branched polycarbodiimide compound (solid content: 20%). Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-2. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 3 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-3) In the same manner as in Synthesis Example 1, a 30% toluene solution 574 of polyhexamethylenecarbodiimide diisocyanate having isocyanate groups at both ends was placed in a condensation reactor. Then, 0.9 parts of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and a 50% toluene solution of polyoxypropylene-polyoxyethylene (50:50) random copolymer monobutyl ether (molecular weight: about 500) was added. Six parts were dropped and reacted. Then, a 50% toluene solution of polyoxyethylene (6) sorbit monolaurate (average number of hydroxyl groups in one molecule: about 5) 5
0.4 part was added dropwise and the reaction was continued. Next, toluene was added to obtain a toluene solution of the branched polycarbodiimide compound (solid content: 20%). Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-3. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 4 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-4) In the same manner as in Synthesis Example 1, 30% propylene glycol monomethyl of polyhexamethylene carbodiimide diisocyanate having isocyanate groups at both ends was added to the condensation reactor. Acetate (hereinafter referred to as PGMEA) solution 574.
0 parts, 0.9 parts of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 50% P of polyethylene glycol monomethyl ether (molecular weight: about 550) was added.
231.0 parts of a GMEA solution was added dropwise and reacted. Next, 50.4 parts of a 50% PGMEA solution of polyoxyethylene (6) sorbit monolaurate was added dropwise, and the reaction was continued. After cooling, PGMEA was added so that the solid content became 20%, and PGME of a branched polycarbodiimide compound was added.
A solution (solid content 20%) was obtained. Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-4. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 5 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-5) In the same manner as in Synthesis Example 1, a 30% PGMEA solution of polytoluylene carbodiimide diisocyanate having isocyanate groups at both ends was added to a condensation reactor. .4 parts, 0.9 parts of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 50% PGMEA of polyethylene glycol monomethyl ether (molecular weight: about 550) was added.
231.0 parts of the solution was added dropwise and reacted. Next, 50% of polyoxyethylene (6) sorbit monolaurate
50.4 parts of the PGMEA solution was added dropwise, and the reaction was continued. After cooling, add PGMEA so that the solid content becomes 20%,
A PGMEA solution of the branched polycarbodiimide compound (solid content: 20%) was obtained. Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-5. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 6 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-6) In the same manner as in Synthesis Example 1, a 30% mineral terpene solution of polytoluylene carbodiimide diisocyanate having isocyanate groups at both ends was placed in a condensation reactor. 376.4
Then, 0.7 part of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 5 parts of oleyl alcohol was added.
61.1 parts of a 0% mineral terpene solution was added dropwise and reacted. Next, 50.4 parts of a 50% mineral terpene solution of polyoxyethylene (6) sorbit monolaurate was added dropwise, and the reaction was continued. After cooling, a mineral terpene was added to a solid content of 20%, and a mineral terpene solution of a branched polycarbodiimide compound (solid content: 20%)
I got Hereinafter, a multi-branched polycarbodiimide-based crosslinking agent-
No. 6. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 7 (Synthesis of Hyperbranched Polycarbodiimide-Based Crosslinking Agent-7) In the same manner as in Synthesis Example 1, a 30% toluene solution 376 of polytoluylene carbodiimide diisocyanate having isocyanate groups at both ends was placed in a condensation reactor. Then, 0.6 part of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 34.2 parts of a 50% solution of n-butanol in toluene was added dropwise to react. Next, 50.4 parts of a 50% toluene solution of polyoxyethylene (6) sorbitol monolaurate was added dropwise, and the reaction was continued. After cooling, toluene was added to a solid content of 20% to obtain a toluene solution of a branched polycarbodiimide compound (solid content: 20%). Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-7. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Synthesis Example 8 (Synthesis of Hyperbranched Polycarbodiimide Crosslinking Agent-8) According to Synthesis Example 1, a 30% PGMEA solution of polytoluylene carbodiimide diisocyanate having isocyanate groups at both ends in a condensation reactor was prepared. 4 parts were charged, 0.9 part of a 5% solution of dibutyltin dilaurate in methyl ethyl ketone was added, and 32.9 parts of a 50% PGMEA solution of triethylamine sulfanilate and 22.2 parts of a 50% PGMEA solution of n-butanol were added dropwise. Reacted. Next, 50.4 parts of a 50% PGMEA solution of polyoxyethylene (6) sorbit monolaurate was added dropwise, and the reaction was continued. After cooling, PGMEA was added to a solid content of 20% to obtain an aqueous solution of a branched polycarbodiimide compound (solid content: 20%). Hereinafter, it is referred to as a hyperbranched polycarbodiimide-based crosslinking agent-8. This compound has a molecular chain having five carbodiimide groups and is reacted so that the total number of carbodiimide groups in one molecule is approximately 14.

Example 1 (Printing on Woven Fabric) 20 parts of a carboxyl group-containing ethyl acrylate-styrene-acrylic acid (60: 36: 4) copolymer latex (solid content: 40%), hyperbranched polycarbodiimide-based cross-linking 5 parts of Agent-1 (solid content: 20%), 10 parts of water and an aqueous solution of polyoxyethylene alkylphenyl ether (solid content: 2
0%) 5 parts were mixed and dissolved, and 55 parts of mineral turpentine was gradually added while stirring with a homomixer to form an O / W emulsion, in which an aqueous dispersion of copper phthalocyanine blue pigment (pigment content 20%) 5 Parts were blended and mixed well to prepare a blue pigment resin printing agent. Print a blue pigment resin printing agent on a cotton knitted cloth with a screen printing machine, and dry at room temperature. Excellent in various fastnesses such as dryness, wet friction fastness, washing fastness and dry cleaning fastness, and it is flexible and coloring. A clear blue printed cloth was obtained. Also, instead of the above-mentioned multi-branched polycarbodiimide-based cross-linking agent-1, multi-branched polycarbodiimide-based cross-linking agents -4, -5 and -6 were used to prepare printing agents, and printing was performed in the same manner as described above. Do
A printed cloth which was excellent in various fastnesses, and was flexible and vivid in color development was obtained.

Example 2 (Waterproof Water Repellent Treatment of Woven Fabric) 90 parts of a solution of butyl acrylate-acrylic acid (95: 5) copolymerized acrylic rubber in ethyl acetate (solid content: 20%)
Hyperbranched polycarbodiimide crosslinking agent-2 (solid content 20
%) In 5 parts of a green solution (10% pigment content, 10% resin content) in which a copper phthalocyanine green pigment is dispersed in an ethyl acetate solution of a butyl acrylate-acrylic acid copolymer.
0 parts were blended and mixed well to prepare a green coating solution. The green coating liquid obtained above on polyester taffeta cloth with a coating machine is coated with resin (wet weight) 3
It was coated at 0 g / m ² , pre-dried at 50 ° C. for 5 minutes, and baked at 130 ° C. for 3 minutes. Next, a toluene solution of a fluorine-silicone resin (solid content: 5%)
And subjected to a water-repellent treatment.

A clear green coated cloth having excellent moisture permeation resistance, water pressure resistance, dryness, fastness to wet friction and fastness to washing was obtained. Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-2, a multi-branched polycarbodiimide-based crosslinking agent-
4, -5, -6, and -7 were used to prepare coating solutions, respectively, and subjected to coating and water-repellent treatment in the same manner as described above to obtain coated fabrics excellent in various fastnesses.

Example 3 (Moisture-permeable coating treatment on woven fabric) A polyurethane polymer dispersion was synthesized. As a glycol component, polytetramethylene glycol (average molecular weight: 1000), ethylene glycol and dimethylolpropionic acid are used, and diphenylmethane diisocyanate is used as a diisocyanate component (molar ratio: 0.1%).
4: 0.3: 0.3: 1.0) and reacted in methyl ethyl ketone to give a milky white polyurethane dispersion (solids 30
%). A polyurethane polymer solution was synthesized. Using a polyoxypropylene-polyoxyethylene block copolymer (70/30) as a glycol component,
Using diphenylmethane diisocyanate as the diisocyanate component (molar ratio: 1: 1), reacting in methyl ethyl ketone, polyurethane solution (solid content 50%)
I got

100 parts of the polyurethane dispersion obtained above,
5 parts of a polyurethane solution and 2 parts of a multi-branched polycarbodiimide-based crosslinking agent-3 are sufficiently mixed, and 120 parts of a mixed solvent of methyl ethyl ketone-toluene-water (weight ratio; 1: 1: 4) is stirred with a homomixer. And uniformly mixed to form a W / O type polyurethane emulsion (solid content 14%)
Was prepared. The W / O type polyurethane emulsion obtained above was applied to the surface of a polyester woven fabric at about 200 g / m ² and dried at 80 ° C. for 3 minutes to form a porous sheet layer. This processed fiber product had excellent water vapor permeability properties and exhibited excellent resistance to dryness and wet abrasion regardless of the porous layer. Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-3, a multi-branched polycarbodiimide-based crosslinking agent-
W / using 4, -5, -6, -7 and -8 respectively
An O-type polyurethane emulsion was prepared, applied and dried in the same manner as described above, to obtain a fiber processed product having excellent water vapor permeability, dry resistance and wet abrasion resistance.

Example 4 (Aqueous adhesive) Polytetramethylene glycol (average molecular weight: about 100)
0) -Dimethylolpropionic acid-isophorone diisocyanate-diethylenetriamine (247: 24: 12
4: 5) 100 parts of an aqueous dispersion (solid content: 40%) obtained by neutralizing the anionic urethane urea resin with triethylamine was added to 100 parts of a multi-branched polycarbodiimide crosslinking agent-1 (solid content: 20%).
%) Was added to prepare an aqueous adhesive composition. Thickness 2
The above aqueous adhesive composition coater was applied to a 0 μm corona discharge treated polypropylene (OPP) film having a wetting index of 40 dynes so as to have a thickness of 2.5 μm in solid content, and immediately after drying, the wetting index was obtained. A 38 dynes 60 μm thick polypropylene (CPP) film was dry laminated at about 60 ° C. using a laminating roll. After aging the laminated film at 40 ° C for 48 hours,
A test piece having a width of 15 mm was prepared, and the adhesive strength was measured at 25 to 26 ° C. using a shipper tester at a tensile strength of 100 mm / min. The result was 173 g / 15 mm.

For comparison, a linear unbranched polycarbodiimide cross-linking agent prepared by using an equivalent amount of diethylene glycol instead of decaglyceryl monolaurate of the above-mentioned multi-branched polycarbodiimide cross-linking agent-1 was used. Was used in place of the multi-branched polycarbodiimide-based cross-linking agent-1, and a laminate film was prepared in the same manner as above, and the adhesive strength was measured in the same manner. As a result, 110 g / 15 m
m. From the above results, it was shown that the adhesive using the multi-branched polycarbodiimide-based cross-linking agent exhibited better adhesiveness than the adhesive using the linear non-branched polycarbodiimide-based cross-linking agent. In addition, instead of the above-mentioned multi-branched polycarbodiimide-based cross-linking agent-1, a water-based adhesive composition was prepared using each of the multi-branched polycarbodiimide-based cross-linking agents -4, -5, and -8, and the same as above. And apply
Lamination was performed to obtain a laminated film having excellent adhesiveness.

Example 5 (Aqueous adhesive) Polycaprolactone diol (average molecular weight: about 2,000)
-1,6-hexanediol-dimethylolpropionic acid-
Toluylene diisocyanate (225: 13: 12: 8
100 parts of an aqueous dispersion (solid content: 40%) obtained by neutralizing the anionic urethane resin of 7) with triethylamine was mixed with 5 parts of a multibranched polycarbodiimide-based crosslinking agent-1 (solid content: 20%).
In addition, an aqueous adhesive composition was prepared. The water-based adhesive composition was applied to an OPP film and dried in the same manner as in Example 4, and a CPP film was dry-laminated.
It was 151 when the adhesive strength of the laminated film was measured.
g / 15 mm.

For comparison, the adhesion of a laminate film obtained by using the linear non-branched polycarbodiimide crosslinking agent used in Example 4 instead of the above-mentioned multibranched polycarbodiimide crosslinking agent-1 The strength was 90 g / 15 mm. Similarly, the adhesive using the multi-branched polycarbodiimide-based cross-linking agent showed excellent adhesiveness as compared with the adhesive using the linear non-branched polycarbodiimide-based cross-linking agent.
Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-1, multi-branched polycarbodiimide-based crosslinking agent-4, -5
And -8 were used to prepare aqueous adhesive compositions, respectively, and applied and laminated in the same manner as above to obtain a laminated film having excellent adhesiveness.

Example 6 (Aqueous Gravure Ink) 40 parts of titanium oxide white pigment, 10 parts of styrene-monobutyl maleate (40:60) copolymer (average molecular weight: about 3500), 10 parts of isopropyl alcohol, and 38 parts of water. 5 parts, pigment dispersant 1 part and silicone defoamer 0.
Five parts of the mixture were ground and dispersed twice using a sand mill to produce a white pigment base color. The above white pigment base color 5
In 0 parts, 40 parts of the aqueous dispersion of anionic urethane urea resin (solid content: 30%) used in Example 4, 0.5 parts of finely divided silicic anhydride, 0.5 parts of polyethylene wax, 0.1 parts of silicone defoamer And 8.9 parts of water, mixed and homogenized with a sand mill, then added and mixed with 1 part of a multi-branched polycarbodiimide-based crosslinking agent-1, and adjusted to pH 8 with aqueous ammonia.
Was adjusted. A nylon film having a thickness of 20 μm was subjected to corona discharge treatment, the white printing ink obtained above was applied using a No. 4 bar coater, dried, and then aged at 40 ° C. for 48 hours. As a result of performing an adhesive strength test of the printing ink layer using a cellophane tape, good results were shown in adhesiveness.

Next, in order to form a laminate film for bag making, 10 parts of a polyester-based adhesive having a carboxyl group (ethyl acetate solution, solid content 63%) and 3.8 parts of a hyperbranched polycarbodiimide-based crosslinking agent-7 were added. The blended adhesive composition for dry lamination was prepared, applied to the white printed surface of the nylon film at a solid content of 3 μm in thickness, and immediately laminated with a corona discharge-treated polypropylene film having a thickness of 60 μm. Laminate film is 40
Aged at 48 ° C for 48 hours. Next, bag making was performed. Tap water was filled in a bag of the laminated film, and a boiling test was performed at about 90 ° C. for 30 minutes. As a result, the surface appearance was good with almost no pinhole-like peeling.

For comparison, the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-1 was replaced with the linear unbranched polycarbodiimide-based crosslinking agent used for comparison in Example 4. Prepare a white printing ink in the same manner as
Printing was performed on a nylon film, and a polypropylene film was further laminated. In the adhesive strength test of the printing ink layer using cellophane tape, the adhesion showed good results, but in the boiling test in which the bag of the laminated film was filled with tap water, pinhole-like peeling was noticeable, and the surface appearance was poor. Wrinkles were noticeable.

From the above results, it is shown that the adhesive using the multi-branched polycarbodiimide-based cross-linking agent exhibits better adhesiveness than the adhesive using the linear non-branched polycarbodiimide-based cross-linking agent. Was done. Also, a white printing ink was prepared using the multi-branched polycarbodiimide-based cross-linking agents -4 and -5 instead of the above-mentioned multi-branched polycarbodiimide-based cross-linking agent-1, and then printed on a nylon film in the same manner. Laminated polypropylene film, excellent adhesion,
A laminate film having boiling resistance was obtained.

Example 7 (aqueous gravure ink) 35 parts of a titanium oxide white pigment, a carboxyl group-containing polyurethane-based aqueous resin obtained from a carbonate-based polyol and an aliphatic isocyanate (solid content: 30%) 50
Parts, water-dispersed wax (solid content 30%) 5 parts, defoamer 1
Part, 9 parts of water and hyperbranched polycarbodiimide-based crosslinking agent-
1 was blended in 5 parts to prepare a white aqueous gravure ink.

Separately, 15 parts of a phthalocyanine blue pigment,
Polyurethane-based aqueous resin containing carboxyl group 60
Parts, 5 parts of a water-dispersed wax, 1 part of an antifoaming agent, 19 parts of water, and 5 parts of a hyperbranched polycarbodiimide-based crosslinking agent-1 to prepare a blue aqueous gravure ink. Polyethylene using the blue and white aqueous gravure ink obtained above,
Gravure printing was performed on a plastic film such as polypropylene, polyester, or nylon. The printed matter obtained was a printed matter for lamination that could withstand boil and retort treatment, and a printed matter that was excellent in heat resistance and chemical resistance in front printing.

Instead of the carboxyl group-containing polyurethane aqueous resin used above, a known carboxyl group-containing acrylic aqueous resin and a carboxyl group-containing polyester aqueous resin-based aqueous gravure ink are used. The printed matter obtained in the same manner was obtained in the same manner as a printed matter for lamination, which was able to withstand the boil and retort treatment, and in the case of front printing, a printed matter having excellent heat resistance and chemical resistance was obtained. Also, a gravure ink was prepared using hyperbranched polycarbodiimide-based crosslinkers -4 and -5 in place of the above-mentioned multibranched polycarbodiimide-based crosslinkers-1,
Similarly, gravure printing was performed on the plastic film, and a printed material for lamination that could withstand boil and retort treatment and a surface printing film excellent in heat resistance and chemical resistance were obtained.

Example 8 (Grain Grain Ink) 12 parts of a vinyl chloride-vinyl acetate-acrylic acid (89: 6.7: 4.3) copolymer having a carboxyl group (average molecular weight: about 30,000) was used. It was dissolved in 71 parts of a mixed solvent of butyl acetate-methyl isobutyl ketone-xylene (43:20:20), added with 2 parts of carbon black pigment, and charged in a ball mill and dispersed for 16 hours. 3 parts of silica was added and mixed, and 12 parts of a hyperbranched polycarbodiimide-based crosslinking agent-2 was further added and mixed to obtain a black gravure ink. Separately, a woodgrain pattern is printed by printing on the surface of a semi-rigid vinyl chloride film that is colored light brown to approximate wood, and a semi-transparent semi-rigid vinyl chloride film is heated and laminated on the surface at the same time as embossing. A recess having a conduit pattern was formed. The average depth of the recess is about 60 to 70 μm.

Next, while the black gravure ink obtained above was allowed to flow over the entire surface, the black gravure ink was applied using a knife coater to fill the recesses formed above with the black ink.
A thin ink layer having a fogging phenomenon of about 1 μm or less was formed on the entire film. Further, a top coat agent comprising an acrylic resin having a carboxyl group and a hydroxyl group on its surface and the multi-branched polycarbodiimide-based cross-linking agent-2 used above is coated with a gravure solid plate to form a top coat layer of about 60 to 70 μm. A wood-grain-printed vinyl chloride sheet with a conduit pattern was formed. The coloring ink and the top coat agent were dried at room temperature, and then aged in a constant temperature room at 30 to 40 ° C. for 3 days.

The sheet obtained as described above is a sheet having a clear wood pattern with a clear pattern without any shrinkage of the sheet and no change in the concave portions, and the pipe pattern has excellent solvent resistance even in a solvent resistance test using a thinner. showed that. Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-2, a multi-branched polycarbodiimide-based crosslinking agent-3, -4, -5, -6
And -7 were used to prepare a gravure ink and a top coat agent, and coated in the same manner to obtain a wood-grained sheet having a clear pattern and excellent solvent resistance.

Example 9 (Coating on Wood Products) 33 parts of a carboxyl group-containing methyl methacrylate-ethyl acrylate-acrylic acid (64: 32: 4) copolymer latex (solid content: 40%), titanium oxide white pigment 2
2 parts, mica 3 parts, talc 7 parts, 3% hydroxyethylcellulose aqueous solution 10 parts, pigment dispersant 1 part, propylene glycol monomethyl ether 1 part, ethylene glycol 2 parts, silicone defoamer 0.5 part, preservative 0. 5 copies,
Hyperbranched polycarbodiimide crosslinking agent-1 (solid content 20
%) And 15 parts of water to prepare a white emulsion paint for outdoor use. Various outdoor buildings were painted white. Since the crosslinking reaction was carried out at room temperature, coating excellent in physical properties such as weather resistance, durability and water resistance could be performed.
Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-1, multi-branched polycarbodiimide-based crosslinking agent-4, -5
And -8 were used to prepare emulsion paints, respectively, and coating with excellent physical properties could be performed in the same manner as described above.

Example 10 (Coating of metal product) 17.9 parts of titanium oxide white pigment, 0.2 part of carbon black pigment, 0.6 part of iron oxide red pigment, methyl methacrylate-ethyl methacrylate-octyl methacrylate-hydroxyethyl methacrylate -Methacrylic acid (4
5: 20: 20: 10: 5) 46.8 parts of a copolymer in ethyl acetate (60% solids), 14 parts of a hyperbranched polycarbodiimide-based cross-linking agent-2 (20% solids), preventing color fading A gray acrylic paint for metal products having a formulation of 0.1 part of the agent and 20.4 parts of xylol was prepared. Gray paint was applied to various machines and office metal products. A coating excellent in physical properties such as weather resistance, durability, and water resistance was able to be applied as a coating which is crosslinked by drying at normal temperature or baking at low temperature. Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-2, a multi-branched polycarbodiimide-based crosslinking agent-
4, -5, -6, and -7 were used to prepare metal product coatings, respectively, and coating with excellent physical properties could be performed in the same manner as described above.

Example 11 (Coating material for vinyl chloride floor material) 95 parts of a carboxyl group-containing polyurethane aqueous resin (solid content: 30%) obtained from carbonate-based polyol and aliphatic isocyanate, 5 parts of silica, 0.5 part of a leveling agent, 0.1 part of an antifoaming agent, and 3 parts of a hyperbranched polycarbodiimide-based crosslinking agent-1 were blended to prepare a coating agent for an aqueous flooring material. Bar coater N for long PVC flooring
Apply to a thickness of about 5 μm using o.
Dried for minutes. To check the effect of the crosslinking agent, a test piece was taken and subjected to a blocking resistance test (30 kg after drying, 2 kg / cm ²
Load, 60 ° C, 48 hours), alcohol resistance test (24 hours after drying, spot test at room temperature for 24 hours)
And a methyl ethyl ketone resistance test (24 hours after drying, a 1 kg / cm ² load, 20 rubbing tests).
In each case, excellent results were obtained as compared with those in which no crosslinking agent was used. In particular, in the blocking resistance test, those not using a crosslinking agent were remarkably inferior and showed a large difference. Further, instead of the above-mentioned multi-branched polycarbodiimide-based crosslinking agent-1, multi-branched polycarbodiimide-based crosslinking agent-4, -5 and -8
Was used to prepare a coating agent for flooring, and coating with excellent physical properties could be performed in the same manner as described above.

Example 12 (Coating of molded polypropylene for bumper) 50 parts of a carboxyl-containing polyurethane-based aqueous resin (solid content: 40%) obtained from carbonate-based polyol and aliphatic isocyanate, 10 parts of talc, 20 parts of calcium carbonate, 5 parts of N-methylpyrrolidone, 1 part of a 5% aqueous solution of hydroxyethyl cellulose, 0.5 leveling agent
Part, aqueous titanium oxide pigment base color (pigment content 65%)
30 parts, 1 part of an aqueous quinacridone red pigment base color (25% pigment content), 100 parts of water, and 2.2 parts of a hyperbranched polycarbodiimide-based crosslinking agent-1 were blended to prepare an aqueous bumper paint. Spray gun on polypropylene molded product for bumper (surface corona treated), dry film thickness about 30
４０40 μm and dried with hot air at 50 ° C. for 15 minutes to obtain a coating film having excellent adhesion and durability. In addition, instead of the above-mentioned multi-branched polycarbodiimide-based cross-linking agent-1, water-based paints were respectively prepared using multi-branched polycarbodiimide-based cross-linking agents-4, -5, and -8, and applied in the same manner as described above. Thus, coating excellent in physical properties could be performed.

[0067]

The metal article, the synthetic resin article of the present invention,
Adhesion or coating of plastic films, wood products, yarns, woven fabrics, non-woven fabrics, papers, and other articles is carried out by using a cross-linking polymer as a cross-linking agent for reactive polymers using a multi-branched polyfunctional carbodiimide compound. Is intended to form a strong bond between the articles or to form a robust coating film on the articles. The carbodiimide compound is a reactive group having a characteristic that the reaction proceeds under normal or low temperature reaction conditions in addition to a compound having high hygiene and safety. However, in the case of linear carbodiimide compounds, post-treatment conditions at room temperature or relatively low temperature often have insufficient cross-linking efficiency and do not contribute to an increase in the density of polymer reticulation. When a functional carbodiimide compound is used, the carbodiimide group itself in each branched molecular chain only partially reacts, and the carbodiimide compound itself becomes a networking center, and further, the carbodiimide group in the same molecular chain and in another molecular chain. As the crosslinking reaction proceeds, the crosslinkable polymer is converted into a crosslinked polymer having a high reticulation density. Due to such a reaction mechanism, it is used for adhesive paints, printing inks, pigment resin printing agents, resin processing agents for textiles, etc. It has the effect of forming a coating film.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshitaka Sebu 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Tatsuo Kawamura 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Eiichi Sugawara 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo (72) Inventor Ken Okura Ken Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Masayuki Takahashi 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Intraday Seika Kogyo Co., Ltd. (72) Inventor Nobuo Takezawa Nihonbashi, Chuo-ku, Tokyo 1-7-6 Bakurocho Dainichi Seika Kogyo Co., Ltd.

Claims (12)

[Claims] 1. A multi-branched polyfunctional polycarbodiimide compound, wherein at least four or more molecular chains having a carbodiimide group are bonded in a branched form. 2. The multi-branched polyfunctional polycarbodiimide compound according to claim 1, wherein the average molecular weight of the multi-branched polyfunctional polycarbodiimide compound is 1,000 to 30,000. 3. An isocyanate compound (a) having at least one carbodiimide group and at least one isocyanate group and a polyol, polyamine and / or a polyol having at least four hydroxyl groups, amino groups and / or imino groups in the molecule. The reaction product according to claim 1, which is a reaction product obtained by reacting with an amino alcohol (b) and, if necessary, further reacting a monoalcohol or a monoamine (c) having one hydroxyl group, amino group or imino group in the molecule. And a multi-branched polyfunctional polycarbodiimide compound. 4. An isocyanate compound (a) having at least one carbodiimide group and at least one isocyanate group and a polyol, polyamine and / or at least four hydroxyl, amino and / or imino groups in the molecule. Reacting with an amino alcohol (b) and, if necessary, further reacting a monoalcohol or a monoamine (c) having one hydroxyl group, amino group or imino group in the molecule. A method for producing a polycarbodiimide compound. 5. A resin composition containing a reactive polymer and a cross-linking agent, wherein the cross-linking agent is an isocyanate compound (a) having one or more carbodiimide groups and one or more isocyanate groups, and 4 A polyol having at least one hydroxyl group, amino group and / or imino group, a polyamine and / or an amino alcohol (b) are reacted with each other, and if necessary, a monomer having one hydroxyl group, amino group or imino group in the molecule. A multi-branched polyfunctional polycarbodiimide compound (A) which is a reaction product obtained by reacting an alcohol or a monoamine (c) with a reactive group having easily transferable hydrogen which can react with the reactive polymer. A resin composition, characterized in that it is a crosslinkable polymer (B). 6. The resin composition according to claim 5, wherein the reactive group having hydrogen which is easily transferred is a reactive group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group. 7. The resin composition according to claim 5, wherein the resin composition is an adhesive, a coating agent, or a resin processing agent for fibers. 8. The resin composition is a colored coating agent obtained by adding a coloring agent to a reactive polymer and a crosslinking agent.
3. The resin composition according to item 1. 9. The resin composition according to claim 5, wherein the resin composition is a paint, a printing ink, or a resin processing agent for pigment resin textile printing fibers. 10. A coating composition containing a reactive polymer and a crosslinking agent thereof, wherein the crosslinking agent is an isocyanate compound (a) having one or more carbodiimide groups and one to two or more isocyanate groups. A polyol, a polyamine and / or an amino alcohol (b) having four or more hydroxyl groups, amino groups and / or imino groups in the molecule are reacted, and if necessary, one hydroxyl group, amino group or imino group is further added to the molecule. A multi-branched polyfunctional polycarbodiimide compound (A), which is a reaction product obtained by reacting a monoalcohol or a monoamine (c) having two or more mono-alcohols or mono-amines (c), and having reactive hydrogen capable of reacting with the reactive polymer. A crosslinkable polymer (B) having a reactive group, and a coating composition prepared by further adding a pigment, a dye, an antifoaming agent, a thickener, a smoothing agent, and the like, if necessary. A method for bonding or coating an article, which comprises applying, printing, impregnating or printing on the article, and drying at room temperature to low temperature and / or heat treatment. 11. The coating composition according to claim 1, wherein the coating composition is a colored coating agent obtained by adding a pigment to a reactive polymer and a crosslinking agent.
10. The method for bonding or coating an article according to item 0. 12. The article is a metal article, a synthetic resin article,
The method for bonding or coating an article according to claim 10, which is an article selected from the group consisting of a plastic film, a wooden product, a thread, a woven fabric, a nonwoven fabric, and paper.