JPH0472318A - Production of polyurethane resin - Google Patents

Abstract

PURPOSE:To extremely easily produce the subject resin having remarkably improved discoloration resistance and excellent mechanical properties and useful for paint, etc., by using a compound having a specific phosphorus-containing polar group and polymerizing in a solvent having low boiling point. CONSTITUTION:The objective resin is produced by reacting (A) a polyol, (B) optionally a chain extender, (C) a polyisocyanate and (D) optionally a chain-end termination agent. At least one of the components A, B and D is a compound having phosphorus-containing polar group expressed by formulas I to VI [R1 is 8-10C trivalent hydrocarbon group; R2 is 1-12C (cyclo)alkyl, aryl, etc.; R3 and R4 are 1-12C (cyclo)alkylene; M is alkali metal or amino] and the polymerization is carried out in a solvent having a boiling point of <70 deg.C (e.g. tetrahydrofuran).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a polyurethane resin that enables stable production at low temperatures.

(Prior Art) Since polyurethane resins have excellent mechanical properties such as toughness, they are used in various applications such as paints, adhesives, coating agents, and binders for magnetic recording media.

Polyurethane resins are produced by polymerization in bulk or in a solvent by adding a solvent such as dibutyltin dilaure F and heating to about 80 to 100'C.

As a solvent, a solvent having a boiling point of about 80° C. or higher, such as methyl ethyl ketone or toluene, is used.

However, if it is necessary to use a low boiling point solvent such as tetrahydrofuran or acetone for various reasons such as coating characteristics, equipment suitability, dispersibility of pigments in paint, drying characteristics, etc., the reaction temperature will exceed approximately 80°C. To ensure the temperature,
This required a pressure cooker, which was disadvantageous in terms of equipment and cost. Furthermore, since the reaction is carried out for a long time at about 80'C or more, the polyurethane resin tends to be colored during polymerization, and the solvent used to promote the reaction has the disadvantage of further promoting the coloring.

(Problems to be Solved by the Invention) In view of the above circumstances, the present inventors have made it possible to produce a polyurethane resin at normal pressure in a solvent with a boiling point of less than 70°C, and which has high stability with little coloration. As a result of intensive studies aimed at obtaining a polyurethane resin that can be soldered, the present invention was achieved.

(Means for Solving the Problems) That is, the present invention provides a polyurethane system in which a polyol (A), an optional chain extender (B), a polyisocyanate compound (C), and an optional terminal capper (D) are reacted. In the method for producing a resin, a compound having a phosphorus polar group of the following (1) to (Vl) in the molecular chain of at least one of the polyurethane-forming components (A), (B) and (D) is used. A method for producing a polyurethane resin, which comprises polymerizing in a solvent with a boiling point of less than 70°C.

R-2Ps 0M (III) (TV) (V) (Vl) The present inventors have developed a method for producing a polyurethane resin using a solvent with a boiling point of less than 70°C, using the formulas (1) to (Vl)
) is used as a polyurethane resin-forming component, and the phosphorus polar group is present in the molecular chain in an amount of 0.5 to 1000 e.
It has been found that by containing q,/10'g, the reactivity between active hydrogen groups such as water fli5 and isonoanate groups, that is, the urethane bond formation reaction, is promoted, and polymerization proceeds even at a low temperature of 40'C.

The polyurethane resin in the present invention is prepared by reacting a polyol resin (A) with a molecular weight of 500 or more, a chain extender (B) with a molecular weight of less than 500, a polyisomer (C), and a terminal capping agent (D) if necessary. As the polyol resin, polyester nol is preferable, and the polyurethane resin is a polyurethane resin obtained by formulas (T) to (V
For the phosphorus polar group represented by l), at least one phosphorus compound having the phosphorus polar group and an ester-forming functional group is used as the carboxylic acid component or glycol component of the polyester diol, or a chain extender is used. It is used as (B) and/or terminal capping agent (D).

The carboxylic acid component of the polyester diol used in the present invention includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid, p-oxybenzoic acid, and p-(hydroxyethoxy)benzoic acid. Aromatic oxycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. Mention may be made of unsaturated aliphatic and cycloaliphatic dicarboxylic acids, tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, and the like.

In addition, the glycol components of polyester diol include ethylene glycol, propylene glycol, 1. G-propanediol, 1.4-butanediol, 1.5-bentanediol, 1.6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,3.4-)dimethyl-1,3-bentane diol, 1,4-cyclohexane dimetatool,
Examples include ethylene oxide and propylene oxide adducts of bisphenol A, ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and other triols and tetraols may be used in combination.Other polyester diols include lactones such as ε-caprolactone, and lactones obtained by ring-opening polymerization. Examples include polyester diols.

The polyisocyanates (C) used in the present invention include 2.4-)lylene diisocyanate, 2.6-tolylene diisonanate, P-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, and tetramethylene. Diisocyanate, 8.8'-Dimethoxy 4', 4-biphenylene diisocyanate, 2
．． 4-naphthalene diisocyanate, 8', 8-dimethyl-4', 4-biphenylene diisocyanate, 4.
4'-diphenylene diisocyanate, 4,4'-diisocyanate-diphenyl ether, 1,5'-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, l,3-diisocyanatemethylcyclohexane, 1,4-diisocyanatemethylcyclohexane , 4,4'-diisocyanate dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate and other diisocyanate compounds, or trimers of 2,4-) lylene diisocyanate, hexa Examples include triisonanate compounds such as a trimer of methylene diisocyanate.

The chain extender (B) with a molecular weight of less than 500 used in the present invention is
It has the effect of adjusting the urethane group or urea group concentration in the resin and imparting toughness unique to polyurethane resins. Specific compounds include ethylene glycol, 1.
3-propylene glycol, 1,4 tetramethylene glycol, 1,6-hexanediol, cyclohexane dimetatool, xylylene glycol, diethylene glycol, triethylene glycol, linear glycols such as ethylene oxide adducts of bisphenol A, propylene glycol, Neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,2,4-trimethyl 1,3-bentanediol, bispheno-JL
/ Branched glycol of propylene oxide adduct of A, amino alcohol such as monoethanolamine, N-methylethanolamine, diamino alcohol such as 2-hydroxytrimethylenediamine, N-hydroxypropylethylenediamine, ethylenediamine, hexamethylenediamine, isophoronediamine , piperazine-4,4
Examples include diamines such as '-diphenylmethanediamine, water, and the like.

Chain extenders other than those listed above include trimethylolpropane, jetanolamine, triethanolamine, glycerin, and other Sannomiya ingredients within a range that does not impair performance, and the total amount of polyester diol (A) and chain extender (B) Equivalent %
May be used below.

If the molecular weight of the chain extender exceeds 500, it is not preferable because the toughness characteristic of polyurethane resins decreases.

One of the forming components of the polyurethane resin of the present invention is a phosphorus compound having a phosphorus polar group and an ester-forming functional group represented by formulas (1) to (Vl) above. The structural formulas of representative examples of these phosphorus compounds are shown below.

NaOOHKOOHOH P (CL(JIzCHzOH) 2 Li P(CHzCthCHzC)IzOH)zNa NHE 3 Na Na HOCHzC1120CHz-P-CToOCHzC)
lzo) lNa CHz ONa CH:+HOCHCH
zOCH2-P-CH2OCH2CHOHP (C8□
CBzCHzOH) z (35) Na K P (CHzCHzC) lzOH)z (36) K Li P (CHzCIIz (JIzOH)z (37) Li ) 100CC) 1. C) 12c11ZOc) 12-P-
C1120CR2C)1. cll,cOO11HoCH
zCHzCjCHx-P-CjbCCHzCHzOH口HOCHzCHzOCHz-P-CHzOC)IzCH
zOHI Open a K In order to further improve the dispersibility of inorganic particles such as magnetic powder, the polyurethane resin of the present invention has a specific polar group that may be copolymerized with a hydrophilic polar-containing compound other than a phosphorus compound. (1)-5o3M, (4) -COOHIn the formula, M represents a hydrogen atom, an alkali metal, tetraalkylammonium, or tetraalkylphosphonium, and RI''
Rs is a hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl,
), which represents aralkyl. Specific compounds are as follows.

(1) -5o, M Polycarboxylic acids and derivatives such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, sodium sulfosuccinic acid, sodium sulfohydroquinone and alkylene oxide adducts,
Sodium sulfobisphenol A and alkylene oxide adducts, etc.

(2) -MR,R, or -N'R+RzRsN-methyljetanolamine, 2-methyl2-dimethylaminomethyl-1,3-propanol, 2-methyl-2-dimethylamino-1,3-propanediol Nitrogen-containing alcohols such as and derivatives thereof.

picolinic acid, dipicolinic acid, aminopyridine, diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridine dimetatool,
Pyridine ring-containing compounds and derivatives thereof, such as pyridine propanediol and pyridine ethanol.

(4) -COOM Glyceric acid, dimethylolpropionic acid, N,N-jetanolglycine, hydroxyethyloxybenzoic acid, hydroxypiparic acid, hydroxypropionic acid, hydroxycarboxylic acid such as hydroxystearic acid, diaminopropionic acid, diamino Examples include aminocarboxylic acids such as benzoic acid and their alkali metal salts. These compounds can be reacted through various processes.For example, they are used as the carboxylic acid component and/or glycol component of polyester polyols, but they can also be used as the chain extender (B) and/or terminal capper (D). can.

The polyaddition reaction of the polyurethane resin of the present invention is carried out by a one-shot method in which all components are reacted simultaneously. First, polyester diol is reacted under conditions with an excess of isocyanate, and the resulting isocyanate group-terminated prepolymer is further processed with a chain extender to further increase the polyester diol. There is a prepolymer method for molecularization.In the case of the polyurethane resin used in the present invention, it can be produced by any method6.The reaction method is carried out by dissolving it in a solution, and the reaction catalyst is stannous octylate, diptylstin. Dilaurate, triethylamine, etc. may also be used.

The obtained polyurethane resin has the above formulas (I) to (Vl)
At least one type of phosphorus polar group represented by 0 is present in the molecular chain.
．． 01=1000eq/10'g, preferably 0.05 to 50eq/10'g, more preferably 0.1 to 5.OeQ/10'g.If it is smaller than the above range, the isocyanate group This is undesirable because the polymerization reaction does not proceed as it loses its catalytic effect in the reaction between the and functional groups having active hydrogen such as hydroxyl groups, and if it exceeds the above range, hygroscopicity increases, physical properties deteriorate, etc., making it impractical. This is not desirable.

When introducing the phosphorus polar groups (1) to (VT) into the polyurethane resin, it is preferable to use polyester diol in terms of solubility in solvents and ease of reaction.

The polyurethane resin of the present invention can be used as a thermoplastic resin as it is, or can be blended with a polyisocyanate compound, a melamine resin, etc. and used as a thermosetting resin.

Furthermore, by introducing unsaturated double bonds into the molecular chains of the polyurethane resin of the present invention, it can be used as a radiation-curable resin that is cured by radiation such as ultraviolet rays, electron beams, gamma rays, and neutron beams. can.

Such a method for producing a radiation-curable resin includes adding one or more unsaturated molecules in the molecule as a chain extender (B) and/or terminal stopper (D) having a molecular weight of less than 500, which are components of the polyurethane resin. A double bond may be reacted with a compound having one or more active hydrogen groups such as a hydroxyl group or an amino group.

Specific compounds include mono(meth)acrylates of glycols such as ethylene glycol, diethylene glycol, and hexamethylene glycol; mono(meth)acrylates and di(meth)acrylates of triol compounds such as trimethylolpropane, glycerin, and trimethylolethane; Poly(meth)acrylates such as mono(meth)acrylates of polyols with a valence of 4 or more such as pentaerythritol and dipentaerythritol, di(meth)acrylates, tri(meth)acrylates, droxyethyl acrylate, hydroquine propyl acrylate, Examples include hydroxyl group-containing acrylic compounds such as (meth)acrylic acid adducts of Epoquin compounds, and amino group-containing acrylic compounds such as (meth)acrylamide, monomethylol (meth)acrylamide, and aminoethyl (meth)acrylate. Further, an acrylic compound containing an isocyanate group such as (meth)acryloyl oxyneethyl isocyanate may be used.

When using ultraviolet rays as radiation, it is desirable to add a photoinitiator to the radiation-curable resin of the present invention. Examples of the photoinitiator include acetophenone, benzophenone, benzoin ethyl ether, benzyl methyl ketal, benzyl ethyl ketal, and benzoin. Isobutyl ketone, hydroxydimethylphenylketone, ■-hydroxycyclohexylphenylketone, 2,2-jethoxyacetophenone, Michler's ketone, 2-hydroxo-2-methylpropiophenone, Hensyl, diethylthioxanthone, 2-chlorothioxane 1-trimethylhendiyldiphenylphosphine oxide, 1-trimethylhendiyldiphenylphosphine oxide, etc. can be used.

Furthermore, a photo-enhancing agent such as n-butylamine, dil-n-butylamine, triethylamine, etc. may be added if necessary.

The polyurethane resin obtained by the production method of the present invention is
Taking advantage of its excellent mechanical properties, it can be used in a variety of applications such as adhesives, coatings, paints, inks, binders for magnetic recording media, and resist materials.

(Implementation N) The present invention will be explained in detail below using examples.

In the examples, parts simply indicate parts by weight.

(Production example of polyester diol) In an autoclave equipped with a thermometer and a stirrer, 357 parts of dimethyl terephthalate and 3 parts of dimethyl isophthalate were added.
57 parts, 65 parts of the phosphorus compound (54), 355 parts of ethylene glycol, 320 parts of neopentyl glycol, and 0.4 parts of tetrabutoquinotitanate.
The mixture was heated at C for 120 minutes to carry out the transesterification reaction.

Next, the temperature of the reaction system was raised to 250"C in 30 minutes, and the pressure in the system was gradually reduced to OwHg after 45 minutes, and the reaction was continued under these conditions for an additional 60 minutes. The molecular weight of the obtained polyester diol A was 2000. , the content of phosphorus compounds is 37
It was 6 eq/l. Polyester diols B-E obtained by a similar manufacturing method are shown in Table 1. The resin composition was analyzed by NMR spectrum.

Below is a blank Table 1 (Examples 1 to 7) Production example of polyurethane resin In a reaction vessel equipped with a thermometer, a stirrer, and a reflux type condenser, 213 parts of tetrahydrofuran, 1.5 parts of the above polyester diol A, and polyester diol E9B , 5th part,
After adding and dissolving 14 parts of hydroxypivalic acid neopentyl glycol ester, 28 parts of 414'-diphenylmethane diisocyanate was processed and reacted at 60°C for 4 hours. The obtained polyurethane resin A showed no coloration (discoloration), had a molecular weight of 20,000, and a phosphorus compound content of 4. It was Oeq/l. Polyurethane resins B-G obtained by a similar method are shown in Table 2.

(Comparative Example 1) In the same reaction vessel as in Example 1, 2 ml of tetrahydrofuran was added.
13 parts, 100 parts of the above polyester diol E, 14 parts of hydroxypivalic acid neopentyl glycol ester
28 parts of 4,4'-diphenylmethane diisocyanate and 0.05 part of diptyltin dilaurate were added and reacted at 60°C for 30 hours, but the polymerization reaction progressed slowly and only a polyurethane resin with a molecular weight of 5000 was obtained. I couldn't.

Table 2 (Examples 8 to 14) Polyurethane acrylate resin production side Into the same reaction vessel as in Example 1, 200 parts of tetrahydrofuran, 1.5 parts of the polyester diol A, and 98.5 parts of the polyester diol E were added and dissolved. After that, 28 parts of 4.4'-diphenylmethane diisocyanate was added, and after reacting at 60°C for 1 hour, 3 parts of glycerin diacrylate was added and further 1
After reacting for hours, 10 parts of hydroxypivalic acid 7-opentyl glycol ester was added, and the mixture was reacted at 60° C. for 3 hours. The obtained polyurethane acrylate resin A showed almost no coloring, had a molecular weight of 15,000, and had a phosphorus compound content of 3.9 eq/l. A third polyurethane acrylate resin B-G obtained by the same method was used.
Shown in the table.

(Comparative Example 2) In the same reaction vessel as in Example 1, 2 ml of tetrahydrofuran was added.
00 parts of the above polyester diol EIO (l) was added and dissolved, 4,4'-diphenylmethane diisocyanate 28
part and 0.05 part of dibutyltin dilaurate, and 60 parts
After reacting for 1 hour at
Although the reaction was carried out for 0 hours, the progress of the polymerization reaction was slow and the molecular weight was 4.
,000 polyurethane acrylate resin was obtained.

Table 3 (Effects of the Invention) According to the method for producing a polyurethane resin of the present invention, a polyurethane resin having a desired molecular weight can be produced extremely easily using a solvent such as tetrahydrofuran with a boiling point of less than 70°C and at normal pressure. By doing so, furthermore, the obtained polyurethane resin is significantly prevented from discoloring. Therefore, the method for producing a polyurethane resin of the present invention has extremely great industrial significance.

Patent Applicant: Toyobo Co., Ltd. Procedural Amendment (White, Yes) November 21, 1990 (1) The "Scope of Claims" in the specification is corrected as shown in the attached sheet.

■ Page 5 lines 1 to 6 of the specification Display of the case 1990 Patent Application No. 1846E35 Name of the invention Person amending the manufacturing method of polyurethane resin Relationship with the case Patent applicant 2-chome Dojimahama, Kita-ku, Osaka “Claims” and “Detailed Description of the Invention” columns of the specification subject to amendment No. 2 No. 8 (If) J (II)
J, page 6, line 10, ro, 5J is corrected to rO, oIJ.

(To) Page 14, lines 1 to 5 (3) “O P (CH2CH2CH20H)2 (42) to 0NH
E, J “Correct to O P (CH2CH2CH20H)2(42).

0NHEt+ ■　Page 14, lines 6-9 rHOcH2CH2 ” \ /11\ NaOOCH2CH2C00CH (45)J rHOcHa CH2 \ Attachment correct.

(■ Correct r-N" RI R2J in the 7th line of page 15 to r-N" R, R2R3J.

ω Same page 15, line 8 Correct r-COOHJ to rcOOMJ.

3) Page 16, line 9 Correct rMR+R2J to rNR, R2J.

Claims: A method for producing a polyurethane resin in which a polyol (A), an optional chain extender (B), a polyisocyanate compound (C), and an optional terminal capper (D) are reacted, the polyurethane-forming component (A), (B)
and the following (1) in at least one molecular chain of (D):
A method for producing a polyurethane resin characterized by using a compound having a phosphorus polar group of ~(II) and polymerizing it in a solvent with a boiling point of less than 70°C 0 (I) u (I [I) (IV ) (V) (Vl)

Claims (1)

[Scope of Claims] A method for producing a polyurethane resin in which a polyol (A), an optional chain extender (B), a polyisocyanate compound (C), and an optional terminal capper (D) are reacted, the polyurethane forming The following (I) is present in at least one molecular chain of the sexual components (A), (B) and (D).
A method for producing a polyurethane resin, which comprises using a compound having a phosphorus polar group (VI) and polymerizing the compound in a solvent having a boiling point of less than 70°C. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) [R_1 is a trivalent hydrocarbon group with 8 to 10 carbon atoms, R_2
represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a cycloalkoxy group, or an aryloxy group. Aryl groups and aryloxy groups include halogen atoms, hydroxyl groups,
-OM'(M' represents an alkali metal) or an amino group bonded thereto may be used. R_3 and R_4 are an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, a group represented by the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (R_5 is an alkylene group having 1 to 12 carbon atoms) , represents a cycloalkylene group, or an arylene group. m is 1 to
It can take any value of 4. ), M represents an alkali metal atom or an amino group. ]