JP2002187932A - Polycarbodiimide compound, method for manufacturing the same and treating method of matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbodiimide compound excellent in storage stability, having a high crosslinking efficiency, and not changing a crosslinked material yellowish, and a method for manufacturing the same. SOLUTION: The polycarbodiimide compound has a number average molecular weight of 300-100,000 and is represented the formula: A-X-R-[N=C=N- R-(X-Y-X-R)-m]-nN=C=N-R-X-A (1) (wherein (m) is an integer of 1-20; (n) is an integer of 1-30; R is an aromatic isocyanate residue, X is a urethane bond; Y is a diol residue; A is a monoalcohol residue.), and is provided by carbodiimidizing a urethane prepolymer having isocyanate groups on the both ends or a prepolymer having an isocyanate group on one end both of which are obtained by reacting an aromatic diisocyanate, a diol, and a monoalcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbodiimide compound which can be used as a crosslinking agent for polymers, a method for producing the same, a treating agent for an article, and a method for treating an article.

[0002]

2. Description of the Related Art Polycarbodiimide compounds generally used include mono- or di-isocyanate compounds.
Conventionally known carbodiimidation catalyst, 3-methyl-1
A method of carbodiimidization using a phosphorene such as -phenyl-2-phospholene 1-oxide, a method of carbodiimidizing a diisocyanate compound with a catalyst, and blocking both ends with a monoalcohol or a monoamine, using an excess of a diisocyanate compound, A method in which a monoalcohol or a monoamine is used to generate an isocyanate at one end and a catalyst is added to form a carbodiimide, a method in which the carbodiimidization proceeds, and a chain is extended using a diol, or a large excess diisocyanate compound is used. And a method of forming a prepolymer with a monoalcohol or a monoamine and adding a catalyst to form carbodiimidization, etc., is used, for example,-(N = C = NR) _n --(N = C = NR) _n -XR'-X- (N = C = N
-R) _n - represented by like (R is a diisocyanate residue in the formula, R '
Is a residue of a diol, and X is a urethane bond. One end of these polycarbodiimide compounds is, for example, Y ′
-X- and the other end are Y'-XR- (Y 'is a monoalcohol or monoamine residue) and the like. As the isocyanate, an aromatic isocyanate and / or an aliphatic isocyanate is used.

[0003]

However, the polycarbodiimide compounds obtained by these methods are:
Carbodiimide group (-N = C = NR-) as described above
A large number of bonds are formed to form a single molecular chain, and when this is used as a cross-linking agent for a polymer such as a resin having a functional group such as a carboxyl group, a cross-linking derived from a carbodiimide group is formed. Although resins and the like are crosslinked, only the properties of the resins and the like and polycarbodiimides alone are exhibited, and properties such as adhesion, adhesion, elongation, and strength may be insufficient depending on the type of the resin. In addition, carbodiimide units that form crosslinks are close to each other, there are many carbodiimide units that do not form crosslinks, and there are cases where the crosslinking efficiency does not increase, and particularly in the case of aromatic carbodiimides, the remaining carbodiimide groups Reacted with alkaline substances and moisture, and yellowed by light. When the amount of the cross-linking agent was reduced to suppress the yellowing, the yellowing was reduced, but the cross-linking efficiency was deteriorated, and properties such as adhesion could not be sufficiently exhibited.

As the isocyanate, an aromatic isocyanate and / or an aliphatic isocyanate is used. When the aromatic isocyanate is used, when the obtained polycarbodiimide compound is used as a crosslinking agent,
Although it exhibited high performance, it lacked storage stability due to its high reactivity, and carbodiimide groups were cyclized during storage, further deteriorating weather resistance. On the other hand, carbodiimide compounds synthesized using aliphatic isocyanates have good storage stability, but when used as a crosslinking agent, have lower reactivity than aromatic carbodiimide compounds,
Sufficient crosslinking performance could not be exhibited.

The present inventors have conducted intensive studies to develop a novel polycarbodiimide compound in which the above-mentioned disadvantages have been improved. As a result, the carbodiimide group was not continuously bonded, but the organic carbodiimide group containing an urethane bond was used. It has been found that the object can be achieved by a polycarbodiimide compound linked via a. The distance between the carbodiimide groups is reduced due to the presence of the organic group, that is, the cross-linking efficiency is improved by increasing the interval between the cross-linking portions, and the carbodiimide group is connected via the organic chain, The polycarbodiimide compound is imparted with flexibility and stretchability derived from organic chains, and more urethane bonds and the like are introduced into the molecular chain than conventional polycarbodiimide compounds, so that the strength, adhesiveness, and elongation are improved. It has been found that the degree of remarkable improvement and the increase in the crosslinking efficiency eliminate the residual carbodiimide group, and the yellowing described above is improved while maintaining the crosslinking performance. In addition, despite the use of aromatic diisocyanates in the production of polycarbodiimide compounds, the resulting polycarbodiimide compounds were also found to have excellent storage stability, and the present invention was completed based on these findings. Was.

[0006]

The above objects are achieved by the present invention described below. That is, the present invention is represented by the following general formula (1) obtained by reacting an aromatic diisocyanate with a diol and a monoalcohol at both terminal isocyanate prepolymers and at one terminal isocyanate prepolymer, and has a number average molecular weight Is 7
A polycarbodiimide compound having a molecular weight of from 100 to 100,000 and a method for producing the same. Wherein m is an integer of 1 to 20, n is an integer of 1 to 30, R
Is a residue of an aromatic isocyanate, X is a urethane bond, Y is
Is a diol residue, and A is a monoalcohol residue. )

Further, the present invention provides a carbodiimidization of an isocyanate prepolymer at both ends and an isocyanate prepolymer at one end obtained by reacting an aromatic diisocyanate with a diol and a monoalcohol, and using this as a chain extender, a dihydric alcohol and A polycarbodiimide compound represented by the following general formula (2) obtained by chain extension with an amine and / or having a number average molecular weight of 700 to 100,000, and a method for producing the same. (In the formula, o is an integer of 1 to 20, p is an integer of 1 to 30, q
Is an integer of 1 to 10, R is a residue of an aromatic isocyanate,
X is a urethane bond, W is a urethane bond and / or a urea bond, Y is a residue of a diol, Z is a residue of a chain extender, and A is a monoalcohol residue. )

[0008]

Next, the present invention will be described in more detail. Each of the polycarbodiimide compounds of the present invention has at least two carbodiimide groups (-N = C =
These carbodiimides are characterized by having a structure in which individual carbodiimide groups are bonded via an organic group such as a urethane bond, instead of being continuously bonded.

The polycarbodiimide compound of the present invention (1)
And (2), for example, by reacting an aromatic diisocyanate compound with a diol and a monoalcohol to synthesize an isocyanate prepolymer at both ends and an isocyanate prepolymer at one end, and performing carbodiimidation using a catalyst; Before completion of the reaction, the remaining isocyanate groups are chain-extended.

In order to connect individual carbodiimide groups via a urethane bond or a diol residue in the present invention, first, an isocyanate prepolymer having both ends of diol reacted with aromatic diisocyanate is prepared. Is important. For this purpose, it is necessary to prepare a prepolymer by reacting the aromatic diisocyanate and the diol at a molar ratio at which both terminals react, and the molar ratio of the aromatic diisocyanate to the diol is determined by the molar ratio of the isocyanate group to the hydroxyl group. The ratio (hereinafter expressed as NCO / OH) is 1 <NCO /
The reaction is performed so that OH ≦ 2.

Further, in order to prevent the individual carbodiimide groups from continuously bonding with each other, the aromatic diisocyanate and the diol are reacted so that the aromatic diisocyanate does not remain in the reaction system, and both ends are surely prevented. It is important to prepare the isocyanate prepolymer. Therefore, the molar ratio of diisocyanate to diol is 1.05 <
NCO / OH <2 is preferred, more preferably 1.25
<NCO / OH <2. At this time, NCO / OH> 2
When reacting with diol using excess aromatic diisocyanate, excess diisocyanate is present in the reaction system, and when carbodiimidation is performed in such a state, carbodiimide chain in which carbodiimide group is continuously bonded to the molecular chain is formed. I can do it. Further, even when the aromatic diisocyanate and the diol are not reacted with each other but are converted into carbodiimide first and then reacted with the diol, a continuous carbodiimide chain is generated.

In the present invention, an aromatic diisocyanate is reacted with a monoalcohol to control the molecular weight to prepare an isocyanate prepolymer at one end, and then carbodiimidated with the isocyanate prepolymer at both ends. In this case, the molar ratio of the total isocyanate groups of the aromatic diisocyanate to the total hydroxyl groups of the diol and monoalcohol is 1 <NCO / OH ≦ 2, preferably 1.05 <NCO / OH <2, more preferably 1.25
<NCO / OH <2. As described above, when the above prepolymer is carbodiimidated, it is necessary to prevent the aromatic diisocyanate from remaining in the reaction system in order to prevent individual carbodiimide groups from continuously bonding. However, when the aromatic diisocyanate remains in the system after the completion of the prepolymer formation reaction, it is important to react by adding a monoalcohol and / or a monoamine corresponding to the amount thereof to deactivate the remaining isocyanate groups. .

The diisocyanate used in the present invention is
It is an aromatic diisocyanate. In the case of an aliphatic diisocyanate, a high temperature or a long time is required for carbodiimidization, and an increase in the amount of a catalyst is required, which is not preferable. The aromatic diisocyanate has the advantage that the carbodiimidization reaction is fast even at a relatively low temperature and that a small amount of catalyst is required. Also, when the generated polycarbodiimide compound is used as a crosslinking agent, the carbodiimide compound obtained using the aromatic diisocyanate has higher reactivity than the carbodiimide compound obtained using the aliphatic diisocyanate, and at room temperature. Reacts easily to give high performance crosslinked products. Therefore, an aromatic carbodiimide compound is preferable to bring out high crosslinking performance. Specific examples of the aromatic diisocyanate include, for example, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate,
p-phenylene diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate
And uretidione such as TDI, and these can be used alone or in combination of two or more. Particularly preferred is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate or a mixture of these in any proportion.

As described above, in the conventional polycarbodiimide compound comprising an aromatic diisocyanate, due to its high reactivity, carbodiimide groups are cyclized and gelation occurs, resulting in poor storage stability. However, even in a polycarbodiimide compound using an aromatic diisocyanate, if there is a substituent at the ortho position with respect to the carbodiimide group, cyclization of the carbodiimide groups is prevented, and gelation is prevented. In the present invention, a prepolymer is prepared by reacting an aromatic diisocyanate with a diol and a monoalcohol. At this time, when an aromatic diisocyanate having an isocyanate group having a different reactivity is used, the prepolymer is selectively converted to a highly reactive isocyanate group. The diol reacts.

For example, when 2,4-toluene diisocyanate is used, the diol selectively reacts with the 4-position isocyanate group, and the remaining 2-position isocyanate group remains. When the 2-position isocyanate group is converted into a carbodiimide, a substituent is introduced at the ortho-position to the carbodiimide group, and the cyclization of the carbodiimide group is prevented by the influence of the substituent, and the storage stability of the polycarbodiimide compound is reduced. As a result, the performance is enhanced. When 2,6-toluene diisocyanate is used, a substituent is always introduced at the ortho position relative to the carbodiimide group. For this reason, in the present invention, 2,4-toluene diisocyanate or 2,6-diisocyanate or a mixture in any proportion thereof is used as a preferred aromatic diisocyanate. An aromatic diisocyanate substituted with a substituent other than a methyl group, for example, an alkyl group such as an ethyl group or a propyl group, or a methoxy group is also effective, but is disadvantageous in that it is expensive. Also, bulky substituents, for example,
In the case of a t-butyl group or the like, steric hindrance to the carbodiimide group is required, and a high temperature or an increase in the amount of catalyst is required for the synthesis of the polycarbodiimide compound. It is not preferable because the property deteriorates.

The diol used in the present invention is preferably an aliphatic or alicyclic diol having 2 to 30 carbon atoms or a mixture thereof. As the above diol, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-
Propanediol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, neo Aliphatic glycols such as pentyl glycol; and alicyclic glycols such as bishydroxymethylcyclohexane and cyclohexane-1,4-diol. Other than these, aromatic glycols such as xylylene glycol and the like can be mentioned. These can be used alone or in combination of two or more.

The monoalcohol used in the present invention includes aliphatic and alicyclic monoalcohols having 1 to 30 carbon atoms, polyalkylene glycol monoalkyl ethers (alkylene chain having 2 to 6 carbon atoms), polyalkylenes. Glycol monoalkyl esters (alkylene chain having 2 to 6 carbon atoms) are preferred. For example, methyl alcohol,
Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, having 2 to 2 carbon atoms
Aliphatic polyalkylene glycol having 4 to 18 carbon atoms, monoether monoalcohols of alicyclic and aromatic hydrocarbon groups, polyalkylene glycol having 2 to 4 carbon atoms having 1 to 18 carbon atoms; Monoester monoalcohols of aliphatic, cycloaliphatic and aromatic monocarboxylic acids are mentioned. These can be used alone or in combination of two or more.

In the present invention, the synthesis of the isocyanate prepolymer at both ends and the isocyanate prepolymer at one end and the carbodiimidization reaction are carried out in a solvent.
As a solvent that can be used, an aprotic solvent having no active hydrogen is used. The solvent used for the carbodiimidization reaction includes a carbodiimidation temperature (usually 60 to 24).
Solvents having a boiling point of 0 ° C. or higher are preferred. In particular,
Aromatic hydrocarbon solvents such as toluene, xylene, swazol (an aromatic hydrocarbon solvent manufactured by Cosmo Oil Co., Ltd.) and Solvesso (an aromatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.); methyl isobutyl ketone; Ketones such as cyclohexanone; esters such as isobutyl acetate; glycol ethers such as diethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate Amide solvents such as dimethylformamide and dimethylacetamide; one or more of dimethylsulfoxide and N-methylpyrrolidone; The synthesis of isocyanates at both terminals and one terminal is usually carried out at 20 to 150 ° C., but the reaction temperature is preferably 20 to 60 ° C. from the viewpoint of easy reaction control.

The both-terminal and one-terminal isocyanate prepolymer synthesized by reacting the aromatic diisocyanate exemplified above with a diol and a monoalcohol is carbodiimidated by the method described below to give the above-mentioned general formula (1). The polycarbodiimide compound of the present invention is synthesized.

On the other hand, the polycarbodiimide compound of the present invention represented by the above general formula (2) can be used for the carbodiimidization of an isocyanate prepolymer having both terminals and one terminal.
Before the isocyanate group is completely carbodiimidated, it can be obtained by chain extension with a chain extender diol and / or diamine. In this case, the reaction conditions before the carbodiimidation are exactly the same as those of the polycarbodiimide compound represented by the general formula (1). Before the end of the carbodiimidization, q in the general formula (2) is 1 to 3 using a diol and / or a diamine as a chain extender.
The chain is extended using an amount such as 10, preferably 1 to 5, more preferably 1 to 3.

As the chain extender used in the present invention, any chain extender conventionally used in the production of polyurethane can be used and is not particularly limited. For example, the aforementioned diols and diamines are used. Examples of the diamine include aliphatic diamines such as ethylenediamine, diaminopropane, diaminobutane, hexamethylenediamine, trimethylhexamethylenediamine, diaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; Heterocyclic diamines such as ethylpiperazine and bis-aminopropylpiperazine; polyoxyethylenediamine, polyoxypropylenediamine,
Polyether diamines such as polyoxyethylene propylene diamine, polyoxyethylene triamine and polyoxypropylene triamine; isophorone diamine;
Alicyclic diamines such as -bisaminomethylcyclohexane and 4,4-diaminocyclohexylmethane; and aromatic diamines such as diaminobenzene and m-xylenediamine. Of these, aliphatic and alicyclic diamines are preferred.

The polycarbodiimide compound of the present invention can be obtained by synthesizing the isocyanate prepolymer at both ends and one end obtained by the above-mentioned method according to a method using a conventionally known carbodiimidization catalyst. That is, for example, 3
By reacting two isocyanate groups of the above prepolymer in the presence of a carbodiimidation catalyst such as -methyl-1-phenyl-3-phospholene-1-oxide (hereinafter referred to as MPPO) to form carbodiimide groups. can get. At the time of carbodiimidization, the amount of MPPO is preferably about 0.1 to 1% by weight, more preferably 0.2 to 0.5% by weight of the charged isocyanate group amount.
If the amount of the catalyst is too small, when carbodiimidization is carried out, when a large number of urethane bonds are present in the isocyanate prepolymer at both ends, a side reaction occurs in which the urethane bond reacts with the isocyanate to form an allophanate bond. In order to suppress this side reaction and promote carbodiimidization, the amount of the catalyst is suitably 0.2 to 0.5% by weight as described above.

The carbodiimidization temperature is usually from 60 to 24.
0 ° C, preferably 100 to 150 ° C, particularly preferably 120 to 140 ° C. If the reaction temperature is too low,
The carbodiimidation does not proceed or the reaction takes time. On the other hand, if the reaction temperature is too high, carbodiimidization proceeds rapidly, but the above-mentioned side reaction of allophanate bond formation occurs, which is not preferable.

The polycarbodiimide compound of the present invention represented by the following general formulas (1) and (2) is obtained by the above carbodimidation reaction. In the above formula, m and o are integers of 1 to 20, n and p are 1
And an integer q is an integer of 1 to 10. R is a residue of an aromatic isocyanate, X is a urethane bond, W is a urethane bond and / or a urea bond, Y is a residue of a diol, A
Represents a residue of a monoalcohol. Q in the general formula (2) indicates the degree of chain elongation.

The values of m and o in the above formula depend on the amounts of diisocyanate and diol used in the preparation of the prepolymer, and the values of n and p are the amount of the prepolymer used in the carbodiimidation, the amount of the catalyst, and the reaction time. And so on. m and o
Exceeds 20, the spacing between the carbodiimide groups is too large, and the crosslinking efficiency may decrease. Preferred m and o are 1-10. On the other hand, when n and p exceed 30, the molecular weight becomes too large, which is not preferable in the crosslinking reaction. Preferred n and p are 1 to 10. On the other hand, if q exceeds 10, the molecular weight increases, which is not preferable in terms of the crosslinking reaction. Preferred q is 1-5.

The number average molecular weight of the carbodiimide compound represented by the above general formulas (1) and (2) (measured by GPC,
(In terms of standard polystyrene) is 300 to 100,00
0, preferably 500 to 20,000, more preferably 1,000 to 10,000. When a carbodiimide compound is used as a cross-linking agent, if the molecular weight is too large, molecular diffusion into a polymer such as a resin is inhibited, and partial cross-linking is likely to occur, thereby affecting various resistances.

The polycarbodiimide compound of the present invention can be used as a crosslinking agent for an article treating agent such as an adhesive, a coating agent, a fiber processing agent, a paint, a printing ink or a pigment resin printing agent. Examples of the polymer used in the treatment agent for such an article include a reactive group having an active hydrogen such as a carboxyl group, a hydroxyl group, a mercapto group, an amino group, or an epoxy group capable of reacting with the carbodiimide group in the polycarbodiimide compound of the present invention. (A cross-linking polymer). Particularly, a polymer having a carboxyl group is preferable. The content of the reactive group in the polymer containing the reactive group varies depending on the type of the reactive group and cannot be unconditionally determined, but is usually about 0.1 to 10% by weight, preferably 0.5 to 5% by weight. It is about.

Examples of the polymer capable of forming a crosslink by reacting with the carbodiimide group (crosslinking-forming polymer) include a conventionally known adhesive, paint, coating agent and the like having the above reactive group.
Polymers used for printing inks, pigment resin printing agents, textile processing agents for waterproofing and water repellency, and the like are used. Specifically, addition polymers such as (meth) acrylate polymers, vinyl polymers, and conjugated diene polymers having the above reactive groups; polyurethane, polyurea, and polyurethane-
Addition condensation polymers such as urea and epoxy resins; condensation polymers such as alkyd resins, polyester resins and polyamide resins; and derivatives of natural products such as rosin-modified resins and cellulose derivative resins. In the present invention, these polymers and natural products are conventionally formed into a film with each of the above treatment agents,
Any of those used as a binder, a vehicle and the like can be used without any particular limitation.

For example, examples of the cross-linking monomer constituting the above-mentioned addition polymer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and esters thereof (hydroxy Alkyl (alkyl group having about 2 to 4 carbon atoms) ester, polyoxyalkylene (alkylene chain having about 2 to 4 carbon atoms) ester, glyceryl ester, etc., monoesters and monoamides of the above-mentioned unsaturated dicarboxylic acids, allyls Alcohol, allylamine and the like.

Examples of the monomer copolymerized with the above-mentioned crosslinking monomer include vinyl monomers such as vinyl chloride, vinyl acetate and styrene; monoolefin monomers such as ethylene; butadiene; Conjugated diene monomers such as isoprene; and alkyl and methacrylate monomers such as alkyl esters of (meth) acrylic acid (where the alkyl group has about 1 to 18 carbon atoms), cyclohexyl esters and benzyl esters. No. These monomers are selected so as to satisfy the performance required for each treating agent, and 1
Species or a mixture of two or more can be used.

The crosslinking-forming addition-condensation polymer or the crosslinking-forming monomer constituting the condensation-polymerization polymer includes, for example, trimellitic anhydride, pyromellitic anhydride, and acid anhydrides thereof. Half esters with diols, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, lysine, arginine, aspartic acid, glutamic acid and the like can be mentioned.

In addition to the above-mentioned polycarbodiimide compound and cross-linking polymer, other components conventionally used in each treating agent can be added to the treating agent of the article of the present invention, if necessary. For example, a non-reactive polymer can be added and used in such a degree that the physical properties of the coating film and the like are not impaired due to the dispersibility of the pigment and the affinity with the article. When the treating agent of the article is used for coloring such as printing inks, pigment resin printing agents and paints, conventionally known pigments, dyes, colored polymer beads, microencapsulated pigments, etc. are added. be able to. Examples of pigments include organic pigments such as phthalocyanine, azo, azomethine azo, azomethine, anthraquinone, and perinone.
Perylene-based, indigo / thioindigo-based, dioxazine-based, quinacridone-based, isoindolinone-isoindoline-based pigments, etc.
Titanium oxide pigments, iron oxide pigments, spinel baked pigments, extender pigments, and the like. When using these pigments in aqueous or solvent-based paints and pigment resin printing agents,
It is preferable to use a high-concentration dispersion color in which a pigment is finely dispersed in advance using a conventionally known surfactant and a water-soluble or solvent-soluble polymer dispersant as a dispersing aid.

The article treating agent of the present invention is used in a form in which these components are dissolved and / or dispersed in an oily solvent or an aqueous solvent. As these solvents, those conventionally used in the above-mentioned processing agents can be used, and there is no particular limitation.
Also, the solid content of the article treating agent is the same as each conventional treating agent, and is not particularly limited.

Next, an example of treatment of the article of the present invention with a treatment agent will be described. A typical treatment is a coating treatment of an article. The articles to be treated are, for example, metal articles, synthetic resin articles, plastic films, wood products, woven fabrics, non-woven fabrics, papers and the like, and specifically, small articles such as iron products and aluminum products; Large articles such as car bodies; metal articles such as buildings; polyethylene, polypropylene, polyvinyl chloride,
Articles made of synthetic resins such as ABS, polyester, and nylon;
Plastic films such as polyethylene, polypropylene, polyvinyl chloride, and polyester; wooden products such as wooden products, plywood products, and wooden structures; and fibrous articles such as yarn, woven fabric, nonwoven fabric, and paper.

The coating treatment is performed by applying, printing, impregnating or printing an article treating agent to these articles. For example, the article treatment agent (coating composition) prepared by adding the polycarbodiimide compound and the cross-linking polymer of the present invention and, if necessary, a pigment, a dye, an antifoaming agent, a thickener, a leveling agent, and the like. An article is coated, printed, impregnated or printed, dried at normal temperature or low temperature, and / or heated to be coated. The polycarbodiimide compound of the present invention as a cross-linking agent has an aromatic carbodiimide group that can react even at a low temperature, and improves the cross-linking efficiency. It is effective for coating or bonding of plastic film products, wood products, large parts, large structures, buildings and other articles such as printing, resin processing, printing and painting.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, parts and percentages are by weight unless otherwise specified.

Example 1 (Polycarbodiimide compound-
1) In a 3-liter separable flask equipped with a condenser, a thermometer and a stirrer, add 2,4-toluene diisocyanate / 2,6-ditoluene diisocyanate (80/2
0 (weight ratio)), and 522 parts of propylene glycol monomethyl ether diacetate (PGMAc).
7.2 parts were charged and stirred and dissolved. Next, a mixture of 480 parts of polyethylene glycol monomethyl ether (PEGME: molecular weight 400) and 108 parts of butanediol was added dropwise at room temperature over 1 hour. Since the reaction is an exothermic reaction, the temperature of the reaction system is adjusted to 40 ° C., and the reaction is carried out at that temperature for 1 hour, and further at 60 ° C. for 1 hour, and the isocyanate prepolymer at both ends is prepared. To prepare a one-terminal isocyanate prepolymer. A part of this was sampled and low molecular weight measurement GPC confirmed that there was no isocyanate monomer. The following examples were confirmed by the same operation.

[0038] The above reaction solution is mixed with the carbodiimidization catalyst 3
-Methyl-1-phenyl-2-phospholene oxide (M
(PPO) was added and heated to 130 ° C. The reaction was carried out while confirming that the isocyanate group was converted to a carbodiimide group by IR. In 3 hours, the peak of the isocyanate group was converted to the peak of the carbodiimide group, and a polycarbodiimide compound was obtained. This is designated as polycarbodiimide compound-1. The solid content of the reaction solution is 5
0.1%. This compound has a calculated molecular weight of 17
In the sample No. 62, the number of carbodiimide groups contained was 2 per molecule. The carbodiimide equivalent (calculated value, the same applies to the following examples) is 881. The number average molecular weight (standard polystyrene conversion) measured by GPC was 2,200. The charged NCO / OH (molar ratio, the same applies to the following examples) = 1.66.

Example 2 (Polycarbodiimide compound-
2) Using the same separable flask as in Example 1,
-500.2 parts of toluene diisocyanate, PGMA
797.1 parts of c were charged. Then 63.12 parts of ethylene glycol, 75.36 parts of butanol and PEGME
A mixture of 212.9 parts (molecular weight: 1000) was dropped and reacted in the same manner as in Example 1, and it was confirmed that there was no isocyanate monomer. Thus, an isocyanate prepolymer at both ends and an isocyanate prepolymer at one end were prepared. One part of MPPO was added to this reaction solution and reacted at 130 ° C. for 2.5 hours until the isocyanate group became a carbodiimide group, to obtain a polycarbodiimide compound. This is designated as polycarbodiimide compound-2. The solid content of the reaction solution is 4
9.8%. This compound has a calculated molecular weight of 12
In 88, there were two carbodiimide groups in one molecule.
The carbodiimide equivalent was 644 and the number average molecular weight measured by GPC was 1875. In addition, NCO of preparation
/OH=1.76.

Example 3 (Polycarbodiimide compound-
3) Using the same separable flask as in Example 1,
539 parts of toluene diisocyanate / 2,6-toluene diisocyanate (8/2 (weight ratio)), PGMA
815.0 parts of c were charged. Then, a mixture of 68.2 parts of ethylene glycol, 51.8 parts of butanol and 219.7 parts of PEGME (molecular weight: 550) was dropped and reacted in the same manner as in Example 1 to confirm that there was no isocyanate monomer. A polymer and a one-terminal isocyanate prepolymer were prepared. 1.62 parts of MPPO was added to the reaction solution and reacted at 130 ° C. for 3 hours until the isocyanate group became a carbodiimide group,
A polycarbodiimide compound was obtained. This is designated as polycarbodiimide compound-3. The solid content of the reaction solution is 50.2%
Met. This compound has a calculated molecular weight of 1483,
The number of carbodiimide groups in one molecule was 6. The carbodiimide equivalent was 570 and the number average molecular weight measured by GPC was 2035. In addition, NCO / OH of preparation =
1.87.

Example 4 (Polycarbodiimide compound-
4) Using the same separable flask as in Example 1,
470 parts of toluene diisocyanate / 2,6-toluene diisocyanate (65/35 (weight ratio))
1031.7 parts of MAc were charged. Then, 144 parts of 2,4-diethyl-1,5-pentanediol (Kyowadiol PD-9 manufactured by Kyowa Hakko Kogyo Co., Ltd.), 60.1 parts of isopropanol and 453 of PEGME (molecular weight 1000) 453 were used.
Parts of the mixture were dropped and reacted in the same manner as in Example 1 to confirm that no isocyanate monomer was present. Thus, a double-ended isocyanate prepolymer and a single-ended isocyanate prepolymer were prepared. 0.94 parts of MPPO was added to the above reaction solution and reacted at 130 ° C. for 3 hours until an isocyanate group became a carbodiimide group, to obtain a polycarbodiimide compound. This is designated as polycarbodiimide compound-4. The solid content of the reaction solution was 50%. This compound had a calculated molecular weight of 2292.3 and had three carbodiimide groups in one molecule. The carbodiimide equivalent is 764. The number average molecular weight measured by GPC was 30,10. NCO / OH = 2
(Molar ratio).

Example 5 (Polycarbodiimide compound-
5) Using the same separable flask as in Example 1,
-522 parts of toluene diisocyanate and 750.5 parts of PGMAc were charged. Subsequently, 125 parts of 3-methyl-1,5-pentanediol and 15 parts of 2-ethylhexanol 15
6.3 parts of the mixture was dropped and reacted in the same manner as in Example 1 to confirm that no isocyanate monomer was present. Thus, a double-terminal isocyanate prepolymer and a single-terminal isocyanate prepolymer were prepared. Add M to the above reaction solution.
One part of PPO was added and reacted at 130 ° C. for 2 hours until the isocyanate group became a carbodiimide group to obtain a polycarbodiimide compound. This is designated as polycarbodiimide compound-5. The solid content of the reaction solution was 48.9%.
This compound had a calculated molecular weight of 1388.8, and contained two carbodiimide groups in one molecule. The carbodiimide equivalent was 669, and the number average molecular weight measured by GPC was 1905. In addition, NCO / OH of preparation =
1.66 (molar ratio).

Example 6 (Polycarbodiimide compound-
6) Using the same separable flask as in Example 1, 2,4-
501.1 parts of toluene diisocyanate, PGMAc7
92.8 parts were charged and stirred. Then 21.6 parts of isopropyl alcohol, 103.7 parts of butanediol and P
A mixture of 216 parts of EGME (molecular weight: 1000) was dropped and reacted in the same manner as in Example 1, and it was confirmed that no isocyanate monomer was present. Thus, a double-terminal isocyanate prepolymer and a single-terminal isocyanate prepolymer were prepared. One part of MPPO was added to the reaction solution, the temperature was raised to 130 ° C., the reaction was performed for 1.5 hours, and the reaction solution was cooled. When a part of this was sampled and the solid content was measured, it was 50%.
The content of unreacted isocyanate groups was 1.525%. Next, 49.0 parts of isophoronediamine, P
49.0 parts of GEAc was gradually added dropwise to extend the chain to obtain a polycarbodiimide compound. This is designated as carbodiimide compound-6. The solid content of the reaction solution was 50.0%. This compound had a calculated molecular weight of 2923 and contained four carbodiimide groups in one molecule. The carbodiimide equivalent is 730.7 and the number average molecular weight determined by GPC is 3856. NCO / O prepared
H = 2 molar ratio).

Comparative Example 1 (Aromatic Polycarbodiimide) As Comparative Example 1, a carbodiimide compound having continuous carbodiimide groups was synthesized. Using the same separable flask as in Example 1, toluene diisocyanate 479.7
Parts, 666 parts of PGMAc, and then butanol 8
A mixture of 8 parts and 189.3 parts of PEGME (molecular weight: 1000) was added dropwise at room temperature over 1 hour. Because there is fever,
After adjusting the temperature to 40 ° C. and reacting at that temperature for 1 hour, 0.5 part of a carbodiimidization catalyst MPPO was added,
Heated to 130 ° C. It was confirmed by IR that no isocyanate monomer was present, and it was confirmed that the isocyanate group had been converted to a carbodiimide group. The solid content of the reaction solution is 5
At 0%, the calculated molecular weight of the resulting compound was 966.3.
And contains three carbodiimide groups in one molecule and has a carbodiimide equivalent of 322.1. The number average molecular weight measured by GPC was 1402. In addition, NCO of preparation
/ OH = 4 (molar ratio).

Comparative Examples 2 and 3 Commercially available aqueous carbodiimide crosslinking agents were used as Comparative Examples 2 and 3. Comparative Example 2 is an aqueous solution of a water-soluble aliphatic carbodiimide (solid content 40%), and Comparative Example 3 is an aliphatic carbodiimide emulsion (solid content 40%).

[Storage stability test] The reaction solutions containing the polycarbodiimide compounds-1 to 6 of Examples 1 to 6 and the aromatic polycarbodiimide of Comparative Example 1 were each adjusted with PGMAc so that the solid content was 40%. did. These reaction solutions and the commercial products of Comparative Examples 2 and 3 were stored at 50 ° C. for one month, and tested for gelation. As a result, no change was observed in Examples 1 to 6 and Comparative Examples 2 and 3, but Comparative Example 1 became a gel. This is probably because the aromatic carbodiimide having no substituent was cyclized. As measured by IR, there was a peak at 1645 cm ^-1 , which was the peak of the cyclized product.

Example 7 (Application to Pigment Resin Printing Agent) The polycarbodiimide compounds of Examples 1 to 6 and Comparative Examples 1 to 3 were used as a crosslinking agent for a binder resin for printing.
Each of the polycarbodiimide compounds of Examples 1 to 6 and Comparative Example 1 used a solution adjusted to have a solid content of 40% with PGMAc. As the polycarbodiimide compounds of Comparative Examples 2 and 3, commercially available products (solid content: 40%) were used as they were.

(1) Preparation of pigment resin printing agent 20 parts of carboxyl group-containing ethyl acrylate / styrene / acrylic acid (60/36/4 (weight ratio)) copolymer latex (solid content 40%), polycarbodiimide compound 5 Parts (in terms of solids), 10 parts of water and 5 parts of a polyoxyethylene alkylphenyl ether aqueous solution (nonionic surfactant: 20% solids) were mixed and dissolved, and 55 parts of a mineral turpent was gradually added while stirring with a homomixer. To prepare an O / W emulsion. An aqueous dispersion of a copper phthalocyanine blue pigment (pigment content: 20
%) And mixed well to prepare a blue pigment resin printing agent.

(2) Evaluation of Pigment Resin Printing Agent Each of the above blue pigment resin printing agents was printed on a polyester cloth using a screen printing machine, dried at room temperature, dried by the following method, and fastened to wet friction and washed. A test of fastness and dry cleaning resistance was performed. Also, the O / W emulsion before adding the pigment was printed on a white polyester woven fabric, and yellowing at room temperature was confirmed. Table 1 shows the test results.

[Various Fastness Testing Methods] (A) Washing Fastness Test A test was conducted in accordance with JIS L-0844 (Method A-4). Using a landometer, put 10 steel balls and a test cloth in an aqueous solution of 0.2% sodium hydrogencarbonate and 0.5% soap, rotate at 70 ° C. for 45 minutes, and visually evaluate the degree of color fading. did. (B) Domestic laundry test A test was performed based on JIS L-0217. Using a household washing machine, bath ratio test cloth / water = 1/30, soap 2
5 minutes washing, dehydration, 2 minutes rinsing,
Dehydration, rinsing for 2 minutes, and dehydration were sequentially performed, and the degree of color fading was visually evaluated.

(C) Friction fastness test A test was conducted in accordance with JIS L-0849. Using a Gakushin type friction fastness tester, load 200 g, amplitude width 10 cm,
Vibration was performed 100 times under the condition of a friction speed of 30 times / minute, and the degree of color loss of the test piece cloth and the degree of contamination on the friction white cloth were visually evaluated. (D) Dry cleaning fastness test A test was conducted based on JIS L-0860. Using a landaumeter, put 20 iron balls and test cloth pieces in a test solution of 100 ml of perclene, 1 ml each of nonionic and anionic surfactants, and 0.1 ml of water, and rotate at 40 ° C. for 30 minutes to remove color. The condition and the degree of contamination of the white part were visually evaluated.

In each test, the evaluation was performed in a five-point scale, and the results are indicated as follows.

(E) Yellowing The printed colorless coating was allowed to stand at room temperature for 3 days to check whether yellowing appeared. O indicates no yellowing, and X indicates yellowing. Table 1 shows the test results.

[0054]

The results in Table 1 show that the polycarbodiimide compound of the present invention and the aromatic polycarbodiimide of Comparative Example 1 each having a crosslinking agent are excellent in various fastnesses, are flexible and have a clear blue color. It shows that a printed cloth was obtained. This is thought to be due to the high reactivity and high adhesion of the aromatic carbodiimide group. However, yellowing does not occur in the polycarbodiimide compound of the present invention, but yellowing occurs in the aromatic polycarbodiimide of Comparative Example 1 in which carbodiimide groups are continuously linked.
This is because the carbodiimide group which did not participate in the crosslinking turned yellow at room temperature due to moisture or light.

Example 8 (Waterproof Water Repellent Treatment of Woven Fabric) Butyl acrylate / acrylic acid (95/5 (weight ratio)) copolymerized acrylic rubber in ethyl acetate (solid content: 2
(0%) and 2.5 parts of a reaction solution (solid content: 40%) of polycarbodiimide compound-5 were mixed with a copper phthalocyanine green pigment in an ethyl acetate solution of the above-mentioned acrylic rubber. Green solution (10% pigment content,
10 parts of a rubber component (10% of rubber) were mixed and sufficiently mixed to prepare a green coating liquid.

30 g (wet weight) of the green coating solution obtained above on polyester taffeta cloth with a coating machine
/ M was coated at a coverage of ^2, after 5 min pre-dried at 50 ° C., was carried out for 3 minutes and baked at 130 ° C.. Next, a toluene solution of a fluorine-silicone resin (solid content: 5%) was padded with this, and a water-repellent treatment was performed. As a result, a clear green coated cloth excellent in moisture permeability, water pressure resistance, dryness, fastness to wet friction and fastness to washing was obtained. Further, the above-mentioned polycarbodiimide compound-5
Instead of polycarbodiimide compounds-1 to -4 and -6
Was used in the same manner as described above to prepare a coating solution, and a coating and a water-repellent treatment were performed. In these cases, a coated cloth having excellent fastness was obtained.

Example 9 (Aqueous adhesive) Polytetramethylene glycol (average molecular weight: about 100)
0) / dimethylolpropionic acid / isophorone diisocyanate / diethylenetriamine (247/24/12
Polycarbodiimide compound-1 was added to 100 parts of an aqueous dispersion (solid content: 40%) obtained by neutralizing an anionic urethane urea resin synthesized by using 4/5 (parts) with triethylamine.
(Solid content: 40%) 2.5 parts was added to prepare an aqueous adhesive composition. Corona discharge treated 20μ thick wetting index 4
The above-mentioned aqueous adhesive composition was applied to a 0-dyne polypropylene (OPP) film using a coater so as to have a dry thickness of 2.5 μm.
Dyne 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 a tensile strength of 100 mm / min.
When the adhesive strength (peel strength) was measured at
It showed 65 g / 15 mm. For comparison, an adhesive composition was prepared using the commercial product of Comparative Example 2 in place of the above-mentioned polycarbodiimide compound-1, and a laminate film was prepared in the same manner as above, and the adhesive strength was measured.
It was 6 g / 15 mm. From the above results, it was shown that the adhesive using the aromatic polycarbodiimide compound exhibited better adhesiveness than the adhesive using the aliphatic polycarbodiimide compound. Further, instead of the above-mentioned polycarbodiimide compound-1, polycarbodiimide compounds-2 to
Using -4 and -6, aqueous adhesive compositions were prepared, respectively, and applied and laminated in the same manner as above to obtain a laminated film having excellent adhesiveness.

Example 10 (aqueous gravure ink) 40 parts of titanium oxide white pigment, 10 parts of styrene / monobutyl ester maleate (40/60 (weight ratio)) (average molecular weight: about 3500), 10 parts of isopropyl alcohol A mixture of 38.5 parts of water, 1 part of a pigment dispersant and 0.5 part of a silicone defoamer was kneaded and dispersed twice by a sand mill to prepare a white pigment base color. 40 parts of the anionic urethane urea resin aqueous dispersion (solid content 30%) used in Example 9 in 50 parts of the above white pigment base color, 0.5 parts of finely divided anhydrous silicic acid, 0.5 parts of polyethylene wax,
0.1 part of a silicone antifoaming agent and 8.9 parts of water are blended, mixed and homogenized by a sand mill, then 1 part of polycarbodiimide compound-2 (solid content: 40%) is added and mixed, and the mixture is adjusted to pH with ammonia water. Was adjusted to 8.

The white printing ink obtained above was applied to a 20 μm thick nylon film subjected to corona discharge treatment with 4
After coating with a bar coater and drying at 25 ° C,
Aged for 8 hours. As a result of measuring the adhesive strength of the printing ink layer by a grid test using cellophane tape, good adhesiveness was shown.

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 1.9 parts of polycarbodiimide compound-5 (solid content 40%). Was prepared, applied to the white printed surface of the nylon film so as to have a dry thickness of 3 μm, and immediately laminated with a corona discharge-treated polypropylene film having a thickness of 60 μm. After the laminated film was aged at 40 ° C. for 48 hours, bag making was performed. Fill the laminated film bag with tap water,
A boiling test was performed for 0 minutes, and the surface appearance was good with almost no pinhole-like peeling.

For comparison, a commercial printing product of Comparative Example 3 was used in place of the above-mentioned polycarbodiimide compound-2 to prepare a white printing ink in the same manner as described above, printed on a nylon film, and laminated with a polypropylene film. .
In the cross-cut adhesive strength test using cellophane tape for the printing ink layer, good adhesion was shown, but the pinhole-like peeling was noticeable in the boiling test in which tap water was filled in a laminate film bag, and the surface appearance Wrinkles were noticeable. From the above results, it was shown that the adhesive using the aromatic polycarbodiimide compound had better adhesiveness than the adhesive using the aliphatic polycarbodiimide compound.

Example 11 (Wooden Gravure Ink) Vinyl chloride / vinyl acetate / acrylic acid (89 / 6.7 / 4.3 (weight ratio)) copolymer having a carboxyl group (average molecular weight is about 30,000) 12 parts of butyl acetate / methyl isobutyl ketone / xylene (43/20/2)
0 (weight ratio)) The mixture was dissolved in 71 parts of a mixed solvent, 2 parts of carbon black pigment was added thereto, and the mixture was charged in a ball mill.
Time dispersed. After further adding and mixing 3 parts of silica,
Six parts of polycarbodiimide compound-3 (solid content 40%) was added and mixed to obtain a black gravure ink.

On the other hand, a woodgrain pattern is printed on the surface of a semi-rigid vinyl chloride film colored in pale brown to approximate a woody material by a printing method, and a semi-transparent semi-rigid vinyl chloride film is laminated on the surface by heating and embossing. A recess having a conduit pattern was formed by processing. The average depth of the recess is about 60 to 70 μm.

Next, the black gravure ink obtained above was applied to the entire surface with a knife coater while flowing down.
The above concave portions were filled with black ink, and 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 compound-3 used above is coated on the surface with a gravure solid plate to form a top coat layer having a thickness of about 60 to 70 μm. Then, 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 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 12 (Coating on Wooden Products) Carboxyl group-containing methyl methacrylate / ethyl acrylate / acrylic acid (64/32/4 (weight ratio)) copolymer latex (solid content: 40%) 33 parts, titanium oxide white Pigment 22 parts, mica 3 parts, talc 7 parts, 3% hydroxyethylcellulose aqueous solution 10 parts, pigment dispersant 1 part,
1 part of propylene glycol monomethyl ether, 2 parts of ethylene glycol, 0.5 part of silicone antifoam, 0.5 part of preservative, polycarbodiimide compound-2 (solid content 40
%) A white emulsion paint for outdoor use was prepared with a formulation of 4 parts and 15 parts of water. Various white buildings were painted white with this emulsion paint. Since the crosslinking reaction was carried out at room temperature, coating excellent in physical properties such as durability and water resistance could be performed. Further, using each of the polycarbodiimide compounds -4 to -6 instead of the above-mentioned polycarbodiimide compound-2, an emulsion paint was prepared in the same manner as described above,
When white coating was performed on various outdoor buildings, coating excellent in physical properties could be performed in the same manner as described above.

Example 13 (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 (weight ratio)) 46.8 parts of a copolymer in ethyl acetate (solid content 60%), 7 parts of polycarbodiimide compound-4 (solid content 40%), anti-discoloration inhibitor A gray acrylic paint for metal products was prepared with a formulation of 0.1 part and 20.4 parts of xylol. When this paint is applied to various machines and office metal products in gray color, it can be applied as a paint that crosslinks by drying at room temperature or baking at low temperature, and has excellent properties such as durability and water resistance. did it.

Example 14 (Coating material for vinyl chloride flooring material) 95 parts of a carboxyl group-containing polyurethane resin aqueous dispersion (solid content: 30%) obtained from carbonate-based polyol and aliphatic isocyanate, silica 5 Parts, 0.5 part of a leveling agent, 0.1 part of an antifoaming agent, and 3 parts of polycarbodiimide compound-1 (solid content: 40%) to prepare a coating agent for an aqueous flooring material.

This coating material was used as a bar coater No. It was applied to a long floor material made of vinyl chloride resin by using No. 10 so as to have a dry thickness of about 5 μm, and dried at 100 ° C. for 1 minute. In order to see the effect of the crosslinking agent, a test piece was taken, a blocking resistance test (applied a load of ² kg / cm ² 30 minutes after drying, and left at 60 ° C. for 48 hours), an alcohol resistance test (24 hours after drying) Then, spot test at room temperature for 24 hours) and methyl ethyl ketone resistance test (24 hours after drying, 1 kg / cm ² load, 20 rubbing tests)
Was done.

As a result, all showed excellent results 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. In addition, the above-mentioned polycarbodiimide compound-
Polycarbodiimide compounds-2, -3 and -in place of 1
5 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 15 (Coating of polypropylene molded article for bumper) 50 parts of an aqueous dispersion of carboxyl group-containing polyurethane resin (solid content: 40%) obtained from carbonate-based polyol and aliphatic isocyanate, talc 10 Parts, calcium carbonate 20 parts, N-methylpyrrolidone 5 parts, hydroxyethyl cellulose 5% aqueous solution 1 part, leveling agent 0.5 part, aqueous titanium oxide pigment base color (pigment 6
5%), 30 parts of an aqueous quinacridone red pigment base color (25% pigment content), 100 parts of water, and 2.2 parts of polycarbodiimide compound-5 (40% solids) were blended to prepare a coating for an aqueous bumper. . It was applied to a polypropylene molded product for bumpers (corona treated on the surface) with a spray gun so as to have a dry film thickness of about 30 to 40 μm, and dried with hot air at 50 ° C. for 15 minutes to obtain excellent adhesion and durability. A coating was obtained.

[0073]

The polycarbodiimide compound using the aromatic diisocyanate of the present invention has at least 2
The compound is a compound having two carbodiimide groups, and the carbodiimide group is not bonded continuously, but is bonded via a urethane bond formed between the diol and the diisocyanate. The carbodiimide groups are bonded while maintaining a certain distance (distance between crosslinking points),
Each carbodiimide group effectively participates in crosslinking and exhibits high crosslinking efficiency. In addition, the carbodiimide group is linked by an organic chain such as a diol residue, thereby imparting flexibility and elongation derived from the organic chain to the polycarbodiimide compound. Furthermore, the high reactivity of the carbodiimide group using an aromatic diisocyanate and the introduction of a larger amount of urethane bonds than the conventional carbodiimide compound cause the polycarbodiimide compound of the present invention to react with the polycarbodiimide compound to form a crosslink. When used as a binder for various applications or as a crosslinking agent for a polymer as a film-forming component, it is possible to form a coating film or printed matter with improved strength, adhesion and adhesion on various articles.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI theme coat ゛ (Reference) C09J 179/00 C09J 179/00 (72) Inventor Tatsuo Kawamura 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Toshio Ishimizu 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Iwao Mihozu Nihonbashi Bakurocho, Chuo-ku, Tokyo 7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Toru Ohura 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo (72) Inventor Mitsuo Toyama Nihonbashi Bakurocho, Chuo-ku, Tokyo 1-7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Michie Nakamura 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo In-house F term (reference) 4J034 AA05 AA06 BA08 CA02 CA04 CC03 CC23 CC26 DG02 HA01 HA07 HB06 HC07 HC08 HC12 HC13 JA42 LA01 LA16 4J038 DG051 DG281 DJ001 GA03 GA11 JB04 KA03 MA06 MA15 NA01 NA10 NA11 NA12 PA19 PCB05P07PC AE04 AE13 BC34 CA04 DA01 EA43 EA46 GA24 4J040 EF051 EF301 EH001 GA05 GA20 HC04 JA02 JA12 JB02 KA25 LA06 MA02 MA08 MA10 MA11 NA10 NA12 NA15 PA30

Claims (10)

[Claims] 1. A carbodiimidized isocyanate prepolymer and an isocyanate prepolymer obtained by reacting an aromatic diisocyanate with a diol and a monoalcohol, represented by the following general formula (1). Is a polycarbodiimide compound of 300 to 100,000. Wherein m is an integer of 1 to 20, n is an integer of 1 to 30, R
Is a residue of an aromatic isocyanate, X is a urethane bond, Y is
Is a diol residue, and A is a monoalcohol residue. ) 2. A carbodiimidization of an isocyanate prepolymer at one end and an isocyanate prepolymer at one end obtained by reacting an aromatic diisocyanate with a diol and a monoalcohol, followed by chain extension with a dihydric alcohol or amine as a chain extender. It is represented by the following general formula (2) and has a number average molecular weight of 300 to 100,00
A polycarbodiimide compound, which is 0. (In the formula, o is an integer of 1 to 20, p is an integer of 1 to 30, q
Is an integer of 1 to 10, R is a residue of an aromatic isocyanate, X is a urethane bond, W is a urethane bond and / or a urea bond, Y is a residue of a diol, Z is a residue of a chain extender, A
Is a monoalcohol residue. ) 3. An aromatic diisocyanate, a diol and a monoalcohol are reacted at a molar ratio of 1 <NCO / OH ≦ 2 to form a isocyanate prepolymer at both ends and an isocyanate prepolymer at one end, followed by carbodiimidization. A method for producing a polycarbodiimide compound, comprising: 4. The method for producing a polycarbodiimide compound according to claim 3, wherein the chain is further extended with a chain extender before the carbodiimidization is completed. 5. The method for producing a polycarbodiimide compound according to claim 3, wherein the aromatic diisocyanate is 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate. 6. The method for producing a polycarbodiimide compound according to claim 3, wherein the diol is a low molecular weight aliphatic or alicyclic diol having 2 to 30 carbon atoms or a mixture thereof. . 7. The monoalcohol is at least one selected from aliphatic and alicyclic monoalcohols having 1 to 30 carbon atoms, polyalkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl esters. The method for producing a polycarbodiimide compound according to any one of the above. 8. The polycarbodiimide compound according to claim 1 or 2 as a cross-linking agent, or the polycarbodiimide compound according to claim 3 or 4.
3. A treating agent for an article, comprising a polycarbodiimide compound obtained by the method described in 1) and a cross-linking polymer having a group reactive with the polycarbodiimide compound. 9. The treatment agent for an article according to claim 8, which is an adhesive, a coating agent, a fiber processing agent, a paint, a printing ink, or a pigment resin printing agent. 10. A method for treating an article, comprising treating the article with the treatment agent according to claim 8.