JPH011717A - Urethane resin colored by chemical bonding - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a urethane resin colored by chemical bonding.

More specifically, a lactone-modified polyol is synthesized by ring-opening addition polymerization of lactones using a line-specific dye containing active hydrogen as an initiator, and colored by chemical bonding. The invention relates to urethane resins.

According to the present invention, it is possible to produce a urethane resin that prevents dye migration by introducing a chromophore into the molecule without using additives such as dyes or pigments.

Urethane resins consisting of polyols such as polyester polyols and polyether polyols obtained through the condensation reaction of polycaprolactone, polysalt II, and diols, organic diisocyanates, and chain extenders are widely used in fields such as elastomers, adhesives, synthetic leather foams, and paints. It is used.

(Prior Art) It is known that polyurethane can basically be colored by adding pigments or dyes to it.

Generally, urethane resin is colored by dispersing pigments or dyes in plasticizers or polyols and reacting them with isocyanate compounds, but this causes various process problems and has a negative effect on the physical properties of the product. There are many things that can be given.

For example, when a urethane resin is colored with a pigment, the resulting product is only slightly colored at a normal pigment concentration, and if a deep shade is desired, a pigment of Comparative Last Winter 8 is required.

On the other hand, when coloring with dyes, the water resistance, oil resistance, migration prevention properties, etc. of the product often become very poor.

Furthermore, when dyes are used as colorants, there is a drawback that the dyes bleed from the colored product and contaminate other materials with which it comes in contact.

However, if the polyurethane is colored with a dye, it is desirable to use a dye rather than a pigment, as it has the advantage of having a clearer color and improved transparency.

However, due to the above-mentioned drawbacks of dyes, pigments are mostly used.

(Problems to be Solved by the Invention) Therefore, there is a strong demand for a urethane resin using a reactive organic dye that has excellent water resistance, oil resistance, and bleed resistance.

Therefore, the inventors of the present invention conducted intensive studies to improve these drawbacks, and as a result, they completed two inventions.

(Structure of the Invention) In other words, the present invention is based on the following formula: ``(a) The following formula % formula % () (where R is a dye group, A is azo, anthraquinone,
Selected from triarylmethane dye groups.

Component A is selected from polyalkylene oxides and copolymers thereof, the alkylene moiety of A has two or more carbon atoms, and A has from about 44 to about 1500 molecules a. n is an integer from 1 to 6.

(X is selected from 1011 groups, -N82 groups, -3H groups)
A colored lactone-modified polyol obtained by reacting 2 moles or more of lactones having 4 to 8 carbon atoms with 1 mole of the organic dye shown in urethane resin colored by chemical bonding.

Next, the present invention will be explained in detail.

A ring-opening initiator for lactone monomers used to synthesize the lactone-modified polyol colored by chemical bonds, which is the first component used in producing the urethane resin colored by chemical bonds of the present invention. Certain dyes are liquid substances at room temperature.

The pigment groups of this liquid organic dye can vary widely, depending largely on the desired color and properties of the final product.

Preferably the interline dye group is attached to A by an amine nitrogen.

Examples of dye groups include nitroso, nitro, azo (including monoazo, diazo and triazo), diarylmethane,
These are triarylmethane, xanthine acrizone, methine, thiazole, indamine, azine, Axazine, or anthraquinone dye group.

Particularly useful in the liquid organic dyes used in this invention are azo, anthraquinone, and triarylmethane dye groups.

The organic dye A used in the present invention is a polymeric epoxide such as polyalkylene oxide and copolymers thereof.

For example, polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of polyethylene oxide, copolymers of polypropylene oxide, copolymers of polybutylene oxide, and the majority of A is polyethylene oxide, polybrobylene oxide, and/or polybutylene oxide. Other copolymers such as block copolymers that are oxides.

Further, this A is about 44 to about 1500, preferably,
10 with an average molecular weight of about 8o to about 800.

Any suitable method may be used to produce liquid reed dyeing 71, which is one of the raw materials for producing the urethane resin of the present invention by bonding A to a dye group.

For example, the method described in US Pat. No. 3,157,663 can be used.

Further, it is desirable to use an inert organic solvent as the reaction medium.

The reason for using a solvent is that when A is bonded to the interrow dye group, it is preferable that it be in a solution state.

Any suitable organic solvent can be used, even aqueous organic solvents.

The hue of the colored polyol, that is, the hue of the final product, urethane resin, basically depends on the pigment group of the selected urethane resin.

By blending two or more types of organic dyes, resins of various hues can be obtained, and blending is easy.

Any suitable method may be used to attach A to the dye group to produce the liquid organic dyes of this invention.

For example, the method described in US Pat. No. 3,157,663 can be used.

Further, it is desirable to use an organic solvent as the reaction medium.

The reason for this is that it is preferable that A, which has a molecular weight within the above-mentioned range, be in a solution state when it is bonded to an important dye group.

Any suitable organic solvent can be used, even aqueous organic solvents.

The hue of organic dyes essentially depends on the dye group chosen.

A variety of colors and hues are obtained by blending two or more organic dyes and are easy to blend.

This existence is caused by the property of Ill.
1 because they are polymers with substantially the same solubility characteristics.

Generally completely compatible with each other.

For example, the liquid organic dye can be produced by adding a dye intermediate containing a primary amino group to the corresponding A compound and using this A compound to MW a compound having a chromophore in the molecule.

In the case of azo dyes, the method consists of reacting a primary aromatic amine with a suitable alkylene oxide or mixture thereof, such as ethylene oxide, propylene oxide or butylene oxide, according to known procedures, and using the resulting compound as a diazonium of the aromatic amine. This is achieved by coupling with salt.

In order to produce a triarylmethane-based liquid organic dye, the aromatic amine reacted with alkylene oxide as described above is combined with an aromatic aldehyde, and the resulting combined product is oxidized to form a triarylmethane-based liquid organic dye. A liquid organic dye is obtained.

Azo-, triphenylmethane-, and anthraquinone-based liquid organic dyes are preferred for reasons such as ease of production, brightness of color, and large amount of phase A obtained, but many other liquid organic dyes are also known. It can be manufactured by

Specific examples of the liquid organic dye used include compounds such as N,N-dihydroxyethylaniline represented by the following formula or N,N-dihydroxyethyl-m-toluidine represented by the following formula.

Suitable lactones used to produce the colored lactone polyol, which is an intermediate for the colored urethane resin of the present invention, include lactones having 4 to 8 carbon atoms.

For example, γ-butyro'lactone, ε-caprolactone, δ
Examples include valerolactone.

Among them, ε-caprolactone is preferred from various points of view.

As a method for producing a lactone-modified polyol, which is an intermediate for the colored urethane resin of the present invention, it is appropriate to use 2 to 50 moles of lactones per mole of the organic dye represented by formula (1).

If the amount is less than 2 moles, the towability of the lactones in the produced lactone adduct will not be sufficiently imparted.

Conversely, if it exceeds 50 moles, the molecule m becomes too large and the viscosity increases during urethane formation, making it difficult to handle.

The reaction temperature is 50°C to 230°C, preferably 13°C.
Heat to 0°C to 220°C.

Below 50°C, the reaction rate becomes extremely slow, and at 220°C
Exceeding this is not preferable because oxycaproic acid is produced by thermal decomposition and the acidity becomes high.

The reaction is preferably carried out at normal pressure and in a nitrogen atmosphere.

Note that it is preferable to include a catalyst in order to promote the reaction during the ring integration.

Examples of catalysts include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate, stannous chloride, stannous bromide, and iodine. First halides such as stannous oxide
Tin etc. are used.

The amount of catalyst added is 0.05 to 1 ooop based on the starting material
pm, preferably 0.1 to 11000 pp.

Catalyst addition 1 to starting material 0. If O is less than 5 ppm, the reaction rate will be slow, and conversely, even if 1100 opp or more is added, the catalyst will only be wasted.

The reaction is completed in 5 to 8 hours, and the unreacted lactone monomer is confirmed to be 1% or less using a gas chromatograph or the like.

For example, when N,N-dihydroxyethylaniline is used as an initiator, the W-treated rough hene polyol 17 has the following structure.

The molecular weight of the colored lactone-modified polyol, which is an intermediate for the urethane resin of the present invention, can be set within a wide range by adjusting the molar ratio of the lactones depending on the use and purpose.

In addition, the colored lactone-modified polyol, which is an intermediate of the urethane resin of the present invention, may be other polyols, such as polycaprolactone, polyester polyol obtained by the condensation reaction of polyHNx and diol, polypropylene glycol, polytetramethylene, etc. It may be used in combination with polyether polyols such as glycols, polycarbonate diols, or copolymer polyols thereof.

The right front diincyanate, which is the second component in the present invention, may be any known organic diisocyanate, such as 2,4 tolylene diisocyanate, 2,6
Tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, carposiimide modified MDI
, xylylene diisocyanate, etc., and one type or two or more types can be used.

The chain extender, which is the third component in the present invention, includes short chain diols and diamines having a primary or secondary terminal amino group.

Suitable chain extenders include short chain diols such as ethylene glycol, diethylene glycol, propylene glycol, 1.4 butanediol and hexanediol, and diamines such as hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine and isophoronediamine. It will be done.

The urethane resin colored by chemical bonding of the present invention is synthesized using each of the components listed above, and its IWNcOI
ndex (for NGO10H) is usually 0.9 to 1.
2. The preferred range is about 0.95 to 1°1.

The production method may be a one-shot method, or a prepolymer method in which a polyol and interline diisocyanate are reacted to produce a prepolymer having a terminal isocyanate, and then a chain extender is added and a chain extension reaction is carried out. Either is fine.

Incidentally, these preparations may be carried out without a solvent or in an inert solvent that does not react with isocyanate groups.

Specific examples of solvents used in this case include toluene, ethyl acetate,
Butyl acetate, methylmorpholine, cyclohequinananone,
Examples include solvents such as dimethylformamide and mixed solvents thereof.

Moreover, a urethanization catalyst can also be used in the urethanization reaction.

Examples include RTj3 tin compounds such as tin octylate and dibutyltin dilaurate, and tertiary amines such as N.methylmorpholine and triethylamine.

Next, the present invention will be explained in detail with reference to Examples.

Synthesis Example-1 In a four-way flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, 51.9 parts (0.1 mol) of the compound of the following formula and 148 parts (1.3 mol) of ε-caprolactone were added.

0.02 part of tetrabutyl titanate was added as a catalyst and reacted for 10 hours at 190°C under a nitrogen atmosphere to produce an amber lactone-modified polyol with a hydroxyl value (R'J) of 56.7 and a waxy state at room temperature. Obtained.

The structural formula of this Rough 1 Hen-modified polyol is estimated to be as follows.

Synthesis Example 2 Into the same apparatus as Synthesis Example 1, 63.7 parts (0.1 mol) of the compound of the following formula, 136.3 parts (1.2 mol) ε-caprolactone, and 0.02 part tetrabutyl titanate as a catalyst were added. was charged and reacted for 30 hours at 150° C. under a nitrogen atmosphere to obtain a yellow, lactone-modified polyol having a hydroxyl value (Nikano/5F) of 57.2 and waxy at room temperature.

The structural formula of this rough modified polyol is estimated to be as follows.

Synthesis Example-3 74.3 parts (0.1 mol) of the compound of the following formula and 0.02 part of tetrabutyl titanate were charged into the same apparatus as Synthesis Example-1, and the hydroxyl value ( Ni Kano my/1
A lactone-modified polyol with a red color of 55.8 in the form of a paste at room temperature was obtained.

The structural formula of this lactone-modified polyol is shown in the following example-
1 198 parts of the colored lactone-modified polyol synthesized in Synthesis Example-1 (0,
1E1), 18 parts (0.2 mol) of 1.4-butanediol
was heated under a nitrogen atmosphere and maintained at 80°C.

Add 75 parts (0.3 mol) of 4,4' diphenylmethane diisocyanate dissolved by heating to 80°C, stir and mix for 5 minutes, and pour into a mold preheated to 80°C. A thermoplastic urethane elastomer of an amber color was obtained by heating and aging at ℃ for 18 hours.

Example-2 196.2 parts (0.1 mol) of colored lactone-modified polyol synthesized in Synthesis Example-2 in the same equipment as in Example-1 and 18 parts (0.2 mol) of 1,4-butanediol. The mixture was heated under a nitrogen atmosphere and maintained at 80°C.

Add 75 parts (0.3 mol) of 4,4-diphenylmethane diisocyanate dissolved by heating at 80°C, and stir for 5 minutes.
The mixture was stirred and mixed, cast into a mold preheated to 80°C, and heated and aged at 80°C for 18 hours to obtain a yellow thermoplastic urethane elastomer.

Example-3 201 parts (0.1 mol) of colored lactone-modified polyol synthesized in Synthesis Example-3 in the same apparatus as Example-1
．． 18 parts (0.2 mol) of 4-butanediol were charged, heated under a nitrogen atmosphere, and maintained at 80°C.

Add 75 parts (0.3 mol) of 4,4-diphenylmethane diisocyanate dissolved by heating to 80°C, stir and mix for 5 minutes, cast into a mold preheated to 80°C, and heat to 80°C for 18 hours. A red thermoplastic urethane elastomer was obtained by heating and aging for several hours.

Patent applicant: Daicel Chemical Industry Co., Ltd. Procedural Amendment (
Spontaneous) September 22, 1985 1, '$Sho Indication 1988 Patent Application No. 158467 2, Title of Invention Urethane Resin Colored by Chemical Bonds 3, Relationship with the Person Making Amendment Case Patent Application Postal code: 590 Address: 1 Chichibo-cho, Sakai City, Osaka Name: (290) Representative: Daicel Chemical Industries, Ltd. Jinke 1) Bibun 5, Contents of amendment (1) Amend the scope of the patent claims as per the attached sheet .

(2) 4th line from the bottom of page 4 of the specification [...organic dye group, A is...] of Correct to [...organic dye group,...].

(3) Second line from the bottom of page 4 of the specification [Ingredient A is...] of [A is...] Correct.

(4) Correct the following formula on page 10, line 7 of the specification.

(5) Lines 9 and 10 of page 10 of the specification are revised to [N,N-dihydroxyethylaniline represented by or the following formula] [EO adduct of aniline represented by or the following formula].

(6) Revise the formula above on the bottom line of page 10 of the specification.

(7) Bottom line of page 10 of Ming Al1I book [N,N-dihydroxyethyl-1-to represented by] of [1-t represented by] Correct.

(8) Page 11, line 1 of the specification [Compounds such as luidine are mentioned. ] and C-luidine such as EO adducts. ] Correct.

(9) Page 13, lines 5 to 6 of the specification [0,・N,N
- dihydroxyethylaniline was used...] was modified to [...aniline E○ adduct was used...].

(1o) Modify the formula to the table of contents on page 13, line 8 of the specification.

(11) Correct the formula above on the second line from the bottom of page 16 of the specification.

(12) Formula at the bottom of page 17 of the specification Correct.

(13) The formula above on the bottom line of page 17 of the specification [ Correct.

(14) Correct the formula above on the third line from the bottom of page 18 of the specification.

(15) The formula above on the 7th line from the bottom of page 19 of the specification.” Correct.

(16) The expression % above the 10th line from the bottom of page 20 of the specification is revised to %.

2. Claims (a) The following formula % formula % () (where R is an organic dye group, and 5A returned from the -azo, anthraquinone, or triarylmethane dye group is a polyalkylene oxide and its selected from copolymers, the alkylene moiety of A having 2 or more carbon atoms,
and A has a molecular weight of about 44 to about 1500. n is an integer from 1 to 6, and X is returned from 10H group, -NH2 group, -3H group).
Colored lactone-modified polyol obtained by reacting 2 moles or more of the lactones (b) organic diincyanate (c) ffl, which is colored by a chemical bond characterized by consisting of a short diol or amine as an extender. Polyurethane resin.

Claims (1)

[Claims] (a) The following formula R-(A-X)n...(I) (where R is an organic dye group, A is azo, anthraquinone,
Selected from triarylmethane dye groups. Component A is selected from polyalkylene oxides and copolymers thereof, the alkylene moiety of A has two or more carbon atoms, and A has a molecular weight of about 44 to about 1,500. n is an integer of 1 to 6, X is -OH group, -NH2 group, -
(b) Organic diisocyanate (c) Short chain extender (b) Organic diisocyanate (c) Short chain extender Urethane resin colored by chemical bonding, characterized by consisting of diols or amines