JPH1160667A - Polycarbodiimide compound, its production, resin composition and treatment of article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycabodiimide compound having excellent sanitariness and storage stability by selecting a compound produced by using an aliphatic hydrocarbon solvent having a specified or higher boiling point as the reaction medium, having a specified number of carbodiimide groups on the average per molecule and having a hydrocarbon group having a specified number of carbon atoms at one molecular terminal. SOLUTION: There is provided a polycarbodiimide compound produced by using an aliphatic hydrocarbon solvent having a boiling point of 120 deg.C or above as the reaction medium, having 2-20 carbodiimide groups on the average per molecule, having a 15-40C hydrocarbon group at least one molecular terminal and having an average molecular weight of 950-10,000. This compound is obtained by reacting a di- or poly-isocyanate compound (e.g. 2,4-toluylene diisocyanate) with a 15-40C aliphatic alcohol (e.g. oleyl alcohol) in a molar ratio of 4/2 in an aliphatic hydrocarbon solvent (e.g. mineral turpentine) and effecting the carbodiimidization of the mixture at 100-150 deg.C in the presence of a 3-methyl-1-phenyl-3-phospholene 1-oxide catalyst.

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 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 resin with the reactive film-forming material. An object of the present invention is to provide a composition and a method for treating an article by using the composition.

[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. In addition, various coating compositions have been used for coating, resin processing, surface coating, and printing articles such as metal articles, synthetic resin articles, plastic films, and wood products. For example, as a binder component as a pigment resin colorant to a woven fabric, an acrylic ester type having a reactive group, a vinyl type, an aqueous emulsion polymerization liquid such as a diene type is used, and a methylol group as a crosslinking agent capable of reacting therewith, Alkylmethylol group,
Epoxy groups, isocyanate groups, ethyleneimine ring groups and the like have been used.

As a paint for metal articles, synthetic resin articles, wood products, etc., and as a gravure printing ink for plastic films, the binder component is a polymer solution such as an acrylic ester, vinyl, diene or the like having a reactive group. In addition, aqueous polymer solutions, aqueous emulsion polymerization liquids and the like have been used, and as the crosslinking agent capable of reacting therewith, similarly, a methylol group, an alkylmethylol group, an epoxy group, an isocyanate group, an ethyleneimine ring group 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 post-treatment temperature is required to cause crosslinking at a low or ordinary temperature.
Regarding hygiene, it is required that the composition is sufficiently sanitary and safe as a treating agent for fibrous articles such as a pigment resin colorant. In the field of paints, there is a demand for inks that can undergo crosslinking at low or ordinary temperature because paints that cannot be subjected to post-processing such as heating, or even in the case of printing, will deform the film. The same applies to hygiene.

[0005] In response to such demands, compounds having a carbodiimide group generated from an isocyanate group are:
It has been found that it can be an excellent crosslinking agent for a reactive polymer having a carboxyl group or the like as a binder, and that the carbodiimide group has higher hygiene and safety than other reactive groups and the like.

[0006]

These carbodiimide compounds have been sufficiently evaluated from the viewpoint of hygiene and safety as compared with the above-mentioned reactive compounds used as conventional crosslinking agents. However, due to the high reactivity of the carbodiimide group, cross-linking may occur during synthesis or storage, which is considered to be an addition reaction between carbodiimide groups, resulting in an increase in the viscosity of the solution or gelation in some cases. was there.

[0007] The same applies to the use. For example, when an aqueous resin composition such as an aqueous pigment printing agent or an aqueous paint is prepared and subjected to an accelerated heating test, a carboxyl group constituting a carboxyl group of the crosslinkable polymer is obtained. Depending on the kind of the acid, it reacts with the carbodiimide group of the water-soluble carbodiimide compound, resulting in a drawback that the viscosity or gelation is caused.

[0008] In view of the above, woven fabric, printing paper,
Paints and prints using cross-linking agents that have excellent robustness to a wide variety of base materials and articles such as wood products and metal products, as well as manufacturing stability, storage stability, and versatility for binders to be compounded. There is a need for the development of coating treatment agents for articles such as ink.

The present inventors have conducted various studies to solve the above-mentioned defects of the aqueous pigment printing agents, coating agents such as paints and printing inks. As a result, the present inventors have found that a crosslinking-forming reactive polymer known as a binder component is used. By using an aliphatic hydrocarbon solvent solution of a polyfunctional polycarbodiimide compound having a hydrocarbon group having 15 to 40 carbon atoms as a crosslinking agent, excellent hygiene, storage stability, against binders to be blended The present invention was found to be excellent in that it has general versatility and the like and can satisfy various physical properties of the obtained resin-processed or colored article.

[0010]

According to the present invention, the boiling point is about 1 unit.
A molecule having an average of 2 to 20 carbodiimide groups in a molecule produced by using an aliphatic hydrocarbon solvent having a temperature of 20 ° C. or higher as a reaction medium, and having a hydrocarbon group having 15 to 40 carbon atoms at least at one end of the molecule. Functional polycarbodiimide compound, method for producing the same using an aliphatic hydrocarbon solvent as a reaction medium, resin composition using the above-mentioned polyfunctional polycarbodiimide compound and a crosslinkable polymer having a reactive group, and articles using the same An object of the present invention is to provide a bonding or coating method.

By forming a network using a highly reactive polyfunctional polycarbodiimide compound which reacts at room temperature as a cross-linking agent, a strong adhesion between articles and a robust coated polymer film on the articles are formed. I tried to make it. However, since the reactivity of the carbodiimide group is high, the viscosity of the solution increases during synthesis or storage, and in some cases, gels, or reacts with the binder when forming the coating composition. There was a risk of thickening or gelling.

However, in the present invention, the boiling point is about 120.
It can be produced very stably using an aliphatic hydrocarbon solvent of at least ℃ as the reaction medium, and has a high storage stability, and should be used as an aliphatic hydrocarbon solvent solution during use. As a result of preparing the above-mentioned crosslinkable polymer and the aqueous resin composition and conducting a heating promotion test, the aqueous resin composition is irrespective of the type of the carboxylic acid constituting the carboxyl group of the crosslinkable polymer. The effect of excellent versatility that neither thickening nor gelation occurs was exhibited.

[0013]

Next, the present invention will be described in more detail with reference to preferred embodiments. The polyfunctional polycarbodiimide compound used in the present invention and which is a cross-linking agent that characterizes the present invention has an average of 2 to 20 carbodiimide groups in a molecule produced using an aliphatic hydrocarbon solvent as a reaction medium as described above. Having at least one carbon end at one end of the molecule.
It is a polycarbodiimide compound having 5 to 40 hydrocarbon groups. The formation reaction of the carbodiimide group of the polyfunctional polycarbodiimide compound is achieved by converting an isocyanate group of di- or polyisocyanate into a carbodiimide group using an aliphatic hydrocarbon solvent as a reaction medium.

The di- or polyisocyanate compound is, for example, 3-methyl-1-phenyl-3-phospholene-1-
In the presence of a carbodiimidation catalyst such as an oxide, approximately 1
The reaction is carried out at a reaction temperature of 00 to 150 ° C. for 5 to 9 hours to decarboxylate two isocyanate groups to form carbodiimide groups. The condensation reaction of the isocyanate group to the carbodiimide group was determined by infrared absorption spectroscopy by confirming the reduction of the isocyanate group and the formation of the carbodiimide group. Although the number of carbodiimide groups in one molecule of the carbodiimide compound is not particularly limited, it is about 2 to 20, preferably about 2 to 10 as an average number because it is a raw material of a crosslinking agent.

The average molecular weight of the polyfunctional polycarbodiimide compound is not particularly limited, but is preferably about 950-10,000, and more preferably about 950-5,000.

Examples of the di- or polyisocyanate compound used include conventionally known aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates. Specifically, for example, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, etc. Examples thereof include polyisocyanate compounds which are dimerized or trimerized by a nurate bond.

The properties of aromatic polycarbodiimide compounds, such as reactivity, storage stability, hot stability, and cold stability, are, for example, toluylene diisocyanate (2,
When the ratio was changed, the reaction time in a mineral terpene medium gradually increased as the amount of 2,6- increased, and the stability time was 2,2.
6- was produced using a substance having a content of 30% or more, was not turbid even after the heating promotion test, was transparent, and returned to a transparent fluid liquid without turbidity even after frozen storage. There was little change in state.

This is because the position of the carbodiimide group or urethane group and the position of the methyl group, that is, the position of the isocyanate group in the aromatic skeleton and the position of the alkyl group greatly affect the stacking property or crystallinity of the resulting compound. It is thought to give. Therefore, the di- or polyisocyanate compound used in the present invention preferably contains about 30% or more of 2,6-toluylene diisocyanate from the viewpoint of stability. Commercially available diisocyanates include toluylene diisocyanate (2,4:
2,6 = 65: 35) is preferable.

Using a mineral terpene with an aliphatic hydrocarbon solvent as a reaction medium, toluylene diisocyanate (2,4: 2,6 = 65: 35) and an aliphatic monoalcohol having a different number of carbon atoms in a molar ratio of 4: 2. The carbodiimidization reaction was further proceeded in the presence of a 3-methyl-1-phenyl-3-phospholene-1-oxide catalyst. What reacted methanol, amyl alcohol, 2-ethylhexanol, and decanol having 10 or less carbon atoms was insoluble, precipitated and separated from the solvent.

The product obtained by reacting lauryl alcohol and myristyl alcohol having 14 or less carbon atoms showed a slight turbidity even when heated, and precipitated and separated at 60 to 40 ° C. The reaction of hexadecanol having 15 to 40 carbon atoms, stearyl alcohol, and oleyl alcohol,
It was in a dissolved state. In particular, oleyl alcohol had an unsaturated group and had no crystallinity, but was reacted. However, the solubility and stability were high, and the state of the solution did not change even when cooled.

From the above results, in the present invention in which an aliphatic hydrocarbon solvent is used as a reaction medium or further as a solvent for a solution, the hydrocarbon group imparting solubility to the hydrocarbon solvent of the carbodiimide compound has about 15 carbon atoms. ~ 40 was found to be necessary. The hydrocarbon group having 15 to 40 carbon atoms is a hydrocarbon group selected from an aliphatic hydrocarbon group having 15 to 40 carbon atoms, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having an aliphatic hydrocarbon group. These groups are obtained by reacting a di- or polyisocyanate with a monoalcohol or monoamine having a hydrocarbon group having 15 to 40 carbon atoms, or converting a monoisocyanate having a hydrocarbon group having 15 to 40 carbon atoms with carbodiimide. It is obtained by performing a reaction for converting to a carbodiimide group by the action of an oxidizing catalyst. The order of the carbodiimidization reaction and the introduction reaction of the hydrocarbon group may be either first or simultaneous.

Examples of the monoalcohol, monoamine or monoisocyanate having a hydrocarbon group having 15 to 40 carbon atoms include, for example, myristyl alcohol, cetyl alcohol, 2-hexyldecanol,
Heptadecanol, stearyl alcohol, oleyl alcohol, behenyl alcohol, melisyl alcohol,
Examples thereof include polyoxyethylene phytosterol, lanosterol, hexadecylamine, stearylamine, abiethylamine, dehydroabiethylamine, and stearylisocyanate.

Examples of the aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or more include, for example, octane, nonane, decane, undecane, dodecane, tridecane, etc., aliphatic petroleum fraction solvents, paraffinic petroleum solvents, isoparaffinic petroleum solvents, Mineral terpenes, mineral spirits and the like.

Conventionally, reaction solvents for the carbodiimidization reaction include aromatic hydrocarbon solvents such as toluene and xylene;
Dioxane, diglyme, ethers such as tetrahydrofuran, ether esters such as propylene glycol monomethyl ether acetate have been proposed,
Aromatic hydrocarbon solvents should be contained as a compounding component of the resin composition, and when used in printing or coating, other than in a work environment where local exhaust is possible, there is a problem in hygiene, and ethers and ethers Esters are soluble in water, and are precipitated by hydrophobic compounds when preparing the aqueous pigment printing agents described above. Depending on the type of acid, etc., it reacts with its carboxyl group,
There is a risk of thickening or gelling. Further, the solvent having a low boiling point is preferably a carbodiimidation reaction of about 100.
It is not preferable because the process proceeds at a temperature of not less than ° C and the solvent evaporates during storage of the solution, and there is a risk of ignition of the volatile solvent.

The purpose of introducing a hydrocarbon group by reacting a di- or polyisocyanate which forms a carbodiimide compound with a monoalcohol, monoamine or monoisocyanate having a hydrocarbon group having 15 to 40 carbon atoms is to use the above-mentioned reaction solvent. To increase the solubility of reaction intermediates and reaction products so that the reaction proceeds smoothly in the prepared aliphatic hydrocarbon solvent, and to enable dissolution as an aliphatic hydrocarbon solvent solution. It is.

In the present invention, the use of polyalcohols, polyamines and / or aminoalcohols having two or more hydroxyl groups, amino groups or imino groups in the molecule together means that the reaction intermediate and the reaction product are fatty acids. The present invention does not hinder the achievement of the present invention as long as it is soluble in the aromatic hydrocarbon solvent.

For example, polyethylene glycols such as ethylene glycol and diethylene glycol, polypropylene glycols such as propylene glycol and dipropylene glycol, butanediol, hexanediol,
Polyglycerols such as trimethylolpropane, glycerin and diglycerin, pentaerythritol, dipentaerythritol, sorbitan, sorbite and the like and amines such as ethylene oxide adduct and propylene oxide adduct thereof, ethylenediamine, propylenediamine, hexamethylenediamine and the like And ethylene oxide adducts and propylene oxide adducts thereof, ethanolamine, diethanolamine, dipropanolamine, and ethylene oxide adducts and propylene oxide adducts of phenolic novolak resins.

After a polycarbodiimide compound is produced using the above-mentioned aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or more as a reaction medium, if necessary, the aliphatic hydrocarbon solvent is distilled out or not without distilling or removing it. Re-dissolve or add a part of it to another solvent such as heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diglyme, triglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, xylene, etc. Use does not prevent achievement of the present invention.

The crosslinkable polymer having a reactive group having a hydrogen which can be reacted and is easily used as the reactive polymer will be described. Examples of the reactive group having an easily-movable hydrogen capable of reacting with the carbodiimide group include a carboxyl group, a hydroxyl group, an amino group, and a thiol group, and a carboxyl group is particularly preferable.

The content of the reactive group having hydrogen which is easily transported and contained in the crosslinkable polymer varies depending on the type of the reactive group, and is not generally determined. 10 to 10% by weight, preferably 0.5 to 5% by weight.

As the crosslinkable polymer, there are used conventionally known adhesives, paints, coatings, printing inks, pigment resin printing agents, fiber resin processing agents, etc. having the above-mentioned reactive groups. A crosslinkable polymer is used. Specifically, polyacrylester-based, polyvinyl-based, and polydiene-based addition polymerization-based polymers each having the above reactive group, polyurethane-based, polyurethaneurea-based, and epoxy resin-based addition-condensation-based polymers, and alkyd resins And polycondensation polymers such as polyesters, polyamides, and the like, rosin-modified resins, and derivatives of natural products such as cellulose derivatives.

Examples of the comonomer having a reactive group having an easily-movable hydrogen used for synthesizing the above-mentioned crosslinkable addition-polymerized polymer include acrylic acid, methacrylic acid and maleic acid. Unsaturated carboxylic acids consisting of, for example, 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 an easily-movable hydrogen used for synthesizing the above-mentioned cross-linkable addition condensation polymer or condensation polymerization polymer is, for example, 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 a coloring agent such as a pigment resin printing agent or a paint is used for coloring purposes, the conventionally known pigments, dyes, colored polymer beads, 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 are described as 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 applying, printing, impregnating, printing or adhering, pressing, or adhering to such an article, will be described. In a coating composition containing a reactive polymer and a crosslinking agent thereof, the crosslinking agent has an average of 2 to 20 carbodiimides in a molecule produced using an aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or higher as a reaction medium. Having at least one end of the molecule having 15 to 4 carbon atoms.
A polyfunctional polycarbodiimide compound having a hydrocarbon group of 0, a cross-linkable polymer having a reactive group having an easily transferable hydrogen capable of reacting with the reactive polymer, and optionally a Applying, printing, impregnating or printing a coating composition prepared by adding a pigment, a dye, an antifoaming agent, a thickener, a smoothing agent, etc. to an article, and drying at room temperature to low temperature and / or heat treatment. This is a method of bonding or coating a featured article.

In particular, the present invention uses a polyfunctional polycarbodiimide compound capable of reacting even at a low temperature, and is preferably a fibrous product, a plastic film product, a wooden product, or a large part, which is preferably subjected to a post-treatment at a temperature from room temperature to 100 ° C. or lower. Printing, resin processing, printing on articles such as large structures, buildings, etc.
It is effective at the time of coating treatment such as painting and bonding or bonding.

[0039]

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 Toluylene diisocyanate-65 (2,4 = 65) was added to a condensation reactor equipped with a stirrer, a thermometer, a moisture meter equipped with a coiled condenser, a nitrogen gas inlet tube and a dropping funnel.
%, 2,6 = 35%) 174.2 parts and mineral terpene (aliphatic hydrocarbon solvent, boiling point: 150 to 200 ° C)
276 parts were charged, and 134.2 parts of oleyl alcohol was added dropwise at room temperature with stirring, and the mixture was stirred and reacted for 1 hour. Subsequently, 3-methyl- as a carbodiimidation catalyst was used.
1-phenyl-3-phospholene-1-oxide 0.08
7 parts, and heated to 120 ° C.
The reaction was performed at 5 ° C. for 7 hours.

The condensation reaction of the isocyanate group with the carbodiimide group was determined by infrared absorption spectroscopy by confirming the reduction of the isocyanate group and the formation of the carbodiimide group. When the isocyanate group became extremely small, 0.9 part of amyl alcohol was added to completely eliminate the isocyanate group, thereby obtaining a mineral terpene solution of a polycarbodiimide compound (solid content: 50%). This compound was reacted so that the number of carbodiimide groups in one molecule was three on average. Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-1.

Synthesis Example 2 Toluylene diisocyanate-65 was reacted with oleyl alcohol in a mineral terpene in the same manner as described in Synthesis Example 1, and then carbodiimide was reacted with a 3-methyl-1-phenyl-3-phospholene-1-oxide catalyst. Then, the remaining isocyanate groups were eliminated with amyl alcohol to obtain a mineral terpene solution of the polycarbodiimide compound. It was charged in a rotary evaporator, and the mineral terpen was distilled off under reduced pressure. There n
-Heptane is added to dissolve the residual resin component, and an n-heptane solution of a polycarbodiimide compound (solid content 50%)
I got This solution tends to volatilize due to the relatively low boiling point of the solvent and is useful during such post-treatment conditions. Less than,
It is called polycarbodiimide-based crosslinking agent-2.

Synthesis Example 3 Toluylene diisocyanate-65 was reacted with oleyl alcohol in a mineral terpene in the same manner as described in Synthesis Example 1, and then carbodiimide was reacted with a 3-methyl-1-phenyl-3-phospholene-1-oxide catalyst. Then, the remaining isocyanate groups were eliminated with amyl alcohol to obtain a mineral terpene solution of the polycarbodiimide compound (solid content: 50%). One part of polyethylene glycol alkyl phenyl ether was dissolved in 40 parts of this mineral terpene solution.

2 parts of polyethylene glycol alkyl phenyl ether is dissolved in 57 parts of water, and the above mineral terpene solution of the polycarbodiimide compound is gradually added while stirring with a homomixer to obtain an oil-in-water (O / W) emulsion ( Content of polycarbodiimide compound: 20
%). Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-3.

Synthesis Example 4 In the same manner as described in Synthesis Example 1, 111.1 parts of isophorone diisocyanate and 300 parts of mineral terpene were charged into a condensation reactor, and oleyl alcohol 13 was added at room temperature.
4.2 parts were dropped and reacted. Then 87.1 parts of toluylene diisocyanate-65 and 3-methyl-1-
0.10 parts of phenyl-3-phospholene-1-oxide was added, the temperature was raised, and a carbodiimidization reaction was performed at 120 to 135 ° C. The remaining isocyanate groups were eliminated with 0.9 parts of amyl alcohol to obtain a mineral terpene solution of the polycarbodiimide compound (solid content: 50%). This compound was reacted so that the number of carbodiimide groups in one molecule was three on average. Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-4.

According to the method described in Synthesis Example 3, water 57
2 parts of polyethylene glycol alkyl phenyl ether was dissolved in the mixture, and the above-mentioned mineral terpene solution of the polycarbodiimide compound was gradually added to the mixture while stirring with a homomixer to prepare an oil-in-water (O / W) emulsion (containing the polycarbodiimide compound). (Amount: 20%). Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-5.

Synthesis Example 5 In the same manner as described in Synthesis Example 1, 87.1 parts of toluylene diisocyanate-65 and 336 parts of mineral terpene were charged into a condensation reactor, and 134.2 parts of oleyl alcohol was added dropwise at room temperature. Reacted. Then 168.2 parts of hexamethylene diisocyanate and 3-methyl-1
0.13 parts of -phenyl-3-phospholene-1-oxide was added, the temperature was raised, and a carbodiimidization reaction was performed at 120 to 135 ° C. The remaining isocyanate groups were eliminated with 0.9 parts of amyl alcohol to obtain a mineral terpene solution of the polycarbodiimide compound (solid content: 50%). This compound was reacted so that the number of carbodiimide groups in one molecule was 5 on average. Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-6.

According to the method described in Synthesis Example 3, water 57
2 parts of polyethylene glycol alkyl phenyl ether was dissolved in the mixture, and the above-mentioned mineral terpene solution of the polycarbodiimide compound was gradually added to the mixture while stirring with a homomixer to prepare an oil-in-water (O / W) emulsion (containing the polycarbodiimide compound). (Amount: 20%). Hereinafter, it is referred to as polycarbodiimide-based crosslinking agent-7.

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%), 12 parts of water and polyoxyethylene 5 parts of an aqueous solution of alkylphenyl ether (solid content: 20%) are mixed and dissolved, and 55 parts of a mineral terpene and 3 parts of a polycarbodiimide crosslinking agent-1 are stirred with a homomixer.
Was gradually added to form an O / W emulsion, and 5 parts of an aqueous dispersion (pigment content: 20%) of a copper phthalocyanine blue pigment was blended and mixed well to prepare a blue pigment resin printing agent.

A blue pigment resin printing agent is printed on cotton cloth and polyester cloth with a screen printing machine, and dried at room temperature, respectively, and is excellent in various fastnesses such as dryness, wet friction fastness, washing fastness and dry cleaning fastness. A flexible and vivid blue printed cloth was obtained.

In preparing the above printing agent, a blue pigment resin printing agent obtained by adding a polycarbodiimide crosslinking agent-4, -6 instead of the polycarbodiimide crosslinking agent-1, or using O / W Using a blue pigment resin printing agent obtained by blending 7.5 parts of an emulsion polycarbodiimide-based crosslinking agent-3, -5, and -7, printing was performed on cotton cloth and polyester cloth, and similarly, excellent in various fastnesses, A flexible and vivid blue printed cloth was obtained.

Example 2 (Waterproof Water-Repellent Treatment of Woven Fabric) 90 parts of a butyl acrylate-acrylic acid (95: 5) copolymerized acrylic rubber in ethyl acetate (solid content: 20%),
10 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 is mixed with 2 parts of a polycarbodiimide crosslinking agent-4. The mixture was mixed well to prepare a green coating liquid.

The green coating solution obtained above was coated on a polyester taffeta cloth with a coating machine at a resin adhesion amount (wet weight) of 30 g / m ² , preliminarily dried at 50 ° C. for 5 minutes, and baked at 130 ° C. for 3 minutes. went. Next, a toluene solution (solid content: 5%) of a fluorine-silicone resin was padded and subjected to a water-repellent treatment. A clear green coated cloth excellent in moisture permeability, water pressure resistance, dryness, fastness to wet friction and fastness to washing was obtained.

Example 3 (Moisture-permeable coating treatment on woven fabric) A polyurethane polymer dispersion and a polyurethane polymer solution to be used were synthesized. As the polyurethane polymer dispersion, polytetramethylene glycol (average molecular weight: 1000), ethylene glycol and dimethylolpropionic acid are used as a glycol component, and diphenylmethane diisocyanate is used as a diisocyanate component (molar ratio: 0.4: 0.3: 0.3: 1.0) Reaction in methyl ethyl ketone to obtain a milky white polyurethane dispersion (solid content 30%).

As the polyurethane polymer solution, a polyoxypropylene-polyoxyethylene block copolymer (70/30) was used as a glycol component, and diphenylmethane diisocyanate was used as a diisocyanate component (molar ratio: 1: 1). The reaction was performed in methyl ethyl ketone to obtain a polyurethane solution (solid content: 50%).

100 parts of the polyurethane dispersion obtained above,
5 parts of polyurethane solution, polycarbodiimide-based crosslinking agent-
2 were sufficiently mixed, and 120 parts of a mixed solvent of methyl ethyl ketone-toluene-water (weight ratio; 1: 1: 4) was added thereto while stirring with a homomixer, and mixed uniformly.
An O-type polyurethane emulsion (solid content 14%) was prepared. The obtained W / O type polyurethane emulsion was applied to the surface of a polyester woven fabric at about 200 g / m ² ,
It dried at 3 degreeC for 3 minutes, and the porous sheet layer was formed. This textile product has excellent water vapor permeability properties,
Excellent dry resistance and wet abrasion resistance were exhibited regardless of the porous layer.

Example 4 (Aqueous adhesive) Polytetramethylene glycol (average molecular weight: about 100)
0) -Dimethylolpropionic acid-isophorone diisocyanate-diethylenetriamine (247: 24: 12
4: 5) Anionic urethane urea resin was neutralized with triethylamine and 100 parts of an aqueous dispersion (solid content: 40%) was added with 10 parts of a polycarbodiimide-based crosslinking agent-3 to prepare an aqueous adhesive composition.

A 20 μm thick corona discharge treated polypropylene (OPP) film having a wetting index of 40 dynes was coated with the above-mentioned aqueous adhesive composition coater to obtain a solid content of 2.
Immediately after drying, a 60 μm thick polypropylene (CP
P) The film was dry-laminated at about 60 ° C. using a laminating roll. Laminated film at 40 ° C
After aging for 48 hours, a test piece having a width of 15 mm was prepared, and a tensile strength of 100 mm / min was measured using a sipper tester.
When the adhesive strength was measured at 25 to 26 ° C, 170 g /
A laminate film having a thickness of 15 mm and having excellent adhesiveness was obtained.

Example 5 (Aqueous adhesive) Polycaprolactone diol (average molecular weight: about 2,000)
-1,6-hexanediol-dimethylolpropionic acid-toluylenediisocyanate-80 (225: 1
3:12:87) An aqueous dispersion (solid content: 40%) obtained by neutralizing an anionic urethane resin with triethylamine.
To 10 parts of a polycarbodiimide-based crosslinking agent-5 was added to prepare an aqueous adhesive composition. The above aqueous adhesive composition was applied to an OPP film and dried in the same manner as in Example 4,
The CPP film was dry laminated. When the adhesive strength of the laminated film was measured, it was 150 g / 15 mm.
showed that.

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.

To 50 parts of the above white pigment base color, 40 parts of the aqueous dispersion of anionic urethane urea resin (solid content: 30%) used in Example 4, 0.5 parts of finely divided anhydrous silicic acid, 0.5 parts of polyethylene wax, Silicone defoamer 0.1
Parts and 8.9 parts of water, mixed with a sand mill and made uniform, and then 3 parts of a polycarbodiimide-based crosslinking agent-3 was added.
After mixing, the pH was adjusted to 8 with aqueous ammonia.

A 20 μm-thick nylon film was subjected to corona discharge treatment, and the white printing ink obtained above was applied with a No. 4 bar coater, dried and then aged at 40 ° C. for 48 hours. As a result of carrying out the adhesive strength test of the printing ink layer using a cellophane tape, good results were shown for the adhesiveness.

Then, in order to form a laminate film for bag making, a dry laminate comprising 10 parts of a polyester-based adhesive having a carboxyl group (ethyl acetate solution, solid content 63%) and 3.8 parts of a polycarbodiimide-based crosslinking agent-2 was blended. An adhesive composition for use 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. The laminated film is 48 at 40 ° C.
After aging for a time, the bag was made. A bag of the laminated film was filled with tap water and subjected to a boiling test at about 90 ° C. for 30 minutes. As a result, it was shown that the surface appearance was good with almost no pinhole-like peeling, and the adhesiveness was excellent.

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
Parts, 9 parts of water and 1 part of polycarbodiimide-based crosslinking agent-7.
2.5 parts of a white aqueous gravure ink were prepared.

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 12.5 parts of a polycarbodiimide-based crosslinking agent-7, to prepare a blue aqueous gravure ink.

Using the blue and white aqueous gravure inks obtained above, gravure printing was performed on a plastic film of polyethylene, polypropylene, polyester, nylon or the like. 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.

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. Add 3 parts of silica, mix, and add 5 parts of polycarbodiimide-based crosslinking agent-6.
Parts were added and mixed to obtain a black gravure ink. Separately,
A wood grain pattern is printed on the surface of semi-rigid vinyl chloride film, which is colored light brown to approximate wood, by a printing method, and a semi-transparent semi-rigid vinyl chloride film is heat-laminated on the surface, and at the same time a conduit pattern is formed by embossing. Was formed. The average depth of the recess is about 60-70μ
It is m-th place.

Next, while applying the black gravure ink obtained above on the entire surface thereof, 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 and the polycarbodiimide-based cross-linking agent-6 used above is coated on 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 duct pattern was obtained. 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 above was a good-looking wood-grained sheet without any shrinkage and no change in the concave portion of the sheet, and the conduit pattern showed excellent solvent resistance even in a solvent resistance test using a thinner. .

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,
10 parts of a polycarbodiimide-based crosslinking agent-5 and 10 parts of water were blended to prepare a white emulsion paint for outdoor use. Various outdoor buildings were painted white. The coating film exhibited excellent properties such as weather resistance, durability and water resistance due to the crosslinking reaction at room temperature.

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 (solid content 60%), 6 parts of polycarbodiimide-based crosslinking agent-4, 0.1 part of anti-fading agent and xylol 28 .4 parts of a gray acrylic paint for metal products were formulated. 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.

Example 11 (Coating material for vinyl chloride flooring material) 80 parts of a carboxyl group-containing polyurethane-based aqueous resin (solid content: 30%) obtained from a carbonate-based polyol and an aliphatic isocyanate, 5 parts of silica, a leveling agent 0.5 part, 0.1 part of an antifoaming agent, 4.4 parts of water and 10 parts of a polycarbodiimide crosslinking agent-5 were blended to prepare a coating agent for an aqueous flooring material. Use a bar coater No. 10 to apply a thickness of about 5 μm to long vinyl chloride floor material,
For 1 minute.

To check the effect of the crosslinking agent, a test piece was taken and
Blocking resistance test (30 kg after drying, 2 kg / cm
² loads, 60 ° C., 48 hours), alcohol resistance test (24 hours after drying, spot test at room temperature for 24 hours) and methyl ethyl ketone resistance test (24 hours after drying, 1 kg / cm ² load, 20 times) Rubbing test)
Was done. 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.

Example 12 (Coating of molded polypropylene for bumper) 50 parts of a carboxyl group-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 11 parts of a polycarbodiimide crosslinking agent-3 were blended to prepare an aqueous bumper paint. A spray gun was used to apply a dry film thickness of about 30 to 40 μm to a molded polypropylene article for bumpers (the surface was corona-treated) with a spray gun and dried with hot air at 50 ° C. for 15 minutes to obtain a coating film having excellent adhesion and durability.

Example 13 An aqueous dispersion of a polyurethane polymer to be used was synthesized. Polycarbonate glycol (average molecular weight: 2,000) and dimethylolpropionic acid are used as the glycol component, and isophorone diisocyanate is used as the diisocyanate component. These are used in a molar ratio of 1.0: 0.8: 2.8.
8 to give a prepolymer having terminal isocyanate groups, further reacting 95% of the terminal isocyanate groups with isophorone diamine and 5% with dibutylamine, then neutralize 95% of the ionic functional groups with triethylamine, An aqueous polyurethane dispersion (solid content: 30%) was obtained.

The aqueous polyurethane dispersion 100 obtained above was used.
Parts, 12.5 parts of polycarbodiimide-based crosslinking agent-3, 50 parts of water, and 5 parts of a pigment aqueous dispersion (pigment content: 20%) were mixed and thoroughly mixed to prepare a colored surface treatment agent for synthetic leather. . The obtained colored surface treatment agents were prepared using the following moisture-permeable urethane synthetic leather fabrics A and B, each having a content of about 10 g /
m ² was applied to obtain respective urethane resin synthetic leather. The synthetic leather colored surface treatment agent had remarkably good stability of the dispersion, and was stable at normal temperature for a pot life of 8 hours or more. The pot life in the case of a colored surface treatment agent using an isocyanate-based crosslinking agent was approximately 4 hours.

The moisture-permeable urethane synthetic leather fabrics A and B used above were prepared as follows. (1) 100 parts of a urethane resin solution for dry-type moisture-permeable synthetic leather,
30 parts of methyl ethyl ketone (MEK) and water / MEK
(10: 1) 55 parts of the mixed solution was thoroughly mixed and 2
Apply to a thickness of 50 μm, 2 minutes at 80 ° C., then 1
Water and MEK were dried stepwise at 30 ° C. for 2 minutes to obtain a moisture-permeable urethane synthetic leather raw fabric A. The moisture permeability was about 8700 g / m ² · 24 hours (resin layer alone). (2) 25 parts of adipate-based thermoplastic urethane resin (100% modulus value: about 40 to 50 kg / cm ² ), 75 parts of dimethylformamide, a desolvation accelerator (surfactant)
3 parts and 5 parts of an aqueous dispersion of a pigment are mixed well, applied to a thickness of 250 μm on a non-woven fabric, the solvent is removed in water to solidify the urethane resin, and the moisture is dried to obtain a transparent foam having open cells. A wet urethane synthetic leather fabric B was obtained.

[0077]

The carbodiimide compound as a cross-linking agent for a cross-linking-forming polymer has high robustness when post-treated at a low temperature or normal temperature, and is more hygienic and safer than conventional cross-linking agents. Although evaluated sufficiently, the viscosity of the solution may increase or gel during synthesis or storage, or the aqueous resin composition prepared using the water-soluble carbodiimide compound may be crosslinked. Depending on the type of the carboxylic acid constituting the carboxyl group of the forming polymer, the heating acceleration test showed a drawback such as thickening or gelling.

The polyfunctional carbodiimide compound of the present invention can be produced very stably using an aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or higher as a reaction medium, and has a high storage stability. The cross-linkable polymer and the aqueous resin composition were prepared using an aliphatic hydrocarbon solvent solution even at the time of use, and as a result of an accelerated test, the amount of the carboxyl group of the cross-linkable polymer was determined. Regardless of the type, the aqueous resin composition exhibited an excellent versatility effect that neither thickening nor gelation occurred.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI C09D 179/00 C09D 179/00 C09J 179/00 C09J 179/00 D06M 15/61 D06M 15/61 (72) Inventor Tatsuo Kawamura Tokyo 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai-Nissei Chemical Industry Co., Ltd. (72) Inventor Eiichi Sugawara 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Dai-Nissei Chemical Industry Co., Ltd. (72) Inventor Yoshiki Konno Tokyo (72) Inventor Toru 1-7-6 Nibashi Bakurocho, Nihonbashi, Chuo-ku, Tokyo 1-7-6 Nikkobashi-cho, Nihonbashi, Nihonbashi, Chuo-ku, Tokyo

Claims (15)

[Claims] An average of 2 to 2 in a molecule produced using an aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or higher as a reaction medium.
A polyfunctional polycarbodiimide compound having 0 carbodiimide groups and having a hydrocarbon group having 15 to 40 carbon atoms at least at one end of the molecule. 2. The aliphatic hydrocarbon solvent is selected from the group consisting of octane, nonane, decane, undecane, dodecane, tridecane, aliphatic petroleum fraction solvents, paraffinic petroleum solvents, isoparaffinic petroleum solvents, mineral terpenes, and mineral spirits. 2. The polyfunctional polycarbodiimide compound according to claim 1, which is one or more selected organic solvents. 3. The hydrocarbon group having 15 to 40 carbon atoms according to claim 1, wherein the hydrocarbon group is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group having an aliphatic hydrocarbon group. A polyfunctional polycarbodiimide compound. 4. The polyfunctional polycarbodiimide composition according to claim 1, wherein the polyfunctional polycarbodiimide compound has an average molecular weight of 950 to 10,000. 5. A molecule having an average of 2 to 20 carbodiimide groups in the molecule, and having at least one end of the molecule having 15 carbon atoms.
A polyfunctional polycarbodiimide composition comprising a polyfunctional polycarbodiimide compound having from 40 to 40 hydrocarbon groups and an aliphatic hydrocarbon solvent. 6. A di- or polyisocyanate and a monoalcohol, monoamine or monoisocyanate having a hydrocarbon group having 15 to 40 carbon atoms using an aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or higher as a reaction solvent. And an isocyanate group is converted into a carbodiimide group by the action of a carbodiimidation catalyst to form an
A polyfunctional polycarbodiimide compound having from 20 to 20 carbodiimide groups and producing the polyfunctional polycarbodiimide compound having the hydrocarbon group having 15 to 40 carbon atoms at least at one of the molecular terminals. Production method. 7. The polyfunctional polycarbodiimide compound according to claim 6, wherein the di- or polyisocyanate is an aromatic di- or polyisocyanate and contains about 30% or more of 2,6-toluylene dipolyisocyanate. Manufacturing method. 8. A resin composition containing a reactive polymer and a crosslinking agent, wherein the crosslinking agent has an average of 2 to 2 in molecules produced using an aliphatic hydrocarbon solvent having a boiling point of about 120 ° C. or higher as a reaction medium. A polyfunctional polycarbodiimide compound having 20 carbodiimide groups and having a hydrocarbon group having 15 to 40 carbon atoms at at least one of the terminal ends of the molecule. A resin composition, which is a crosslinkable polymer having a reactive group having hydrogen. 9. The resin composition according to claim 8, wherein the reactive group having hydrogen which is easily transferred is a reactive group selected from a reactive group consisting of a carboxyl group, a hydroxyl group, and an amino group. 10. The resin composition according to claim 8, wherein the resin composition is an adhesive, a coating agent, or a resin processing agent for fibers. 11. The resin composition according to claim 8, wherein the resin composition is a colored coating agent obtained by adding a coloring agent to a reactive polymer and a crosslinking agent. 12. The resin composition according to claim 8, wherein the resin composition is a paint, a printing ink or a resin processing agent for a pigment resin textile printing fiber. 13. A coating composition comprising a reactive polymer and a crosslinking agent thereof, wherein the crosslinking agent has a boiling point of about 120 ° C.
A polyfunctional compound having an average of 2 to 20 carbodiimide groups in a molecule produced using the above aliphatic hydrocarbon solvent as a reaction medium, and having a hydrocarbon group having 15 to 40 carbon atoms at least at one end of the molecule. A polycarbodiimide compound, a cross-linkable polymer having a reactive group having a readily transferable hydrogen capable of reacting with the reactive polymer, and, if necessary, a pigment, a dye, an antifoaming agent, and a thickening agent. A coating composition prepared by adding an agent, a leveling agent, etc., to an article, printing, printing, impregnating or printing, and drying at room temperature or low temperature and / or heat treatment. . 14. 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.
4. The method for bonding or coating an article according to item 3. 15. The method according to claim 13, wherein the article is an article selected from the group consisting of a metal article, a synthetic resin article, a plastic film, a wooden product, a thread, a woven fabric, a nonwoven fabric, and a paper. Coating method.