JPH0796644B2 - Polyurethane resin composition and manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane resin composition useful as a paint (for example, a magnetic paint), a vehicle for coating, an adhesive, and a production method.

[Prior Art] Conventionally, as a production technology of a non-aqueous dispersion or powder of a polyurethane resin, there is one that uses polyacrylate or polyester as a dispersion stabilizer. (For example, JP-A-49-52295
(Japanese Patent Laid-Open No. 48-16999). [Problems to be Solved by the Invention] However, these have the problem of poor dispersion stability.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of extensive studies on a polyurethane resin composition which has good dispersion stability and can be used for the production of both non-aqueous dispersions and powders.

That is, the present invention comprises a polyol (a), a polyisocyanate (b) and an active hydrogen-containing compound (c) having a functional group selected from the group consisting of the following (c ₁ ), (c ₂ ) and (c ₃ ). Polyurethane characterized by comprising a urethane polymer (I), a polyol (a ') as a dispersion stabilizer, a polyisocyanate (b') and a long-chain active hydrogen-containing aliphatic hydrocarbon derivative (II) the resin composition _{(c 1) -COOX (c 2} ) -SO 3 X (c 3) -PO (OX) 2 X = H, metal salt, NH ₄ or amine cation: presence of a dispersion stabilizer according to claim 1, wherein Below, a polyol (a), a polyisocyanate (b) and an active hydrogen-containing compound (c) having a functional group are reacted in a non-polar solvent to separate the non-polar solvent, thereby producing a powdery polyurethane resin. Is the law

Polyols (a), (a ') used in the present invention
Examples include polyether diols and polyester diols.

Examples of polyether diols include low molecular weight glycols [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octamethylene. Diols, alkyl dialkanol amines; low molecular weight diols having a cyclic group [for example, those described in JP-B-45-1474: bis (hydroxymethyl) cislohexane, m- and p-xylylene glycol, bis (hydroxyethylbenzene, 1, 4-bis (2-hydroxyethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) -diphenylpropane (ethylene oxide adduct of bisphenol A), etc.], and mixtures of two or more thereof] (Alkyleneoxy having 2 to 4 carbon atoms Sid: ethylene oxide, propylene oxide, 1,2-, 2,3-, 1,3-butylene oxide, etc.) adduct, and alkylene oxide, cyclic ether (tetrahydrofuran, etc.) ring-opening polymerization or ring-opening copolymerization (block and And / or random), for example polyethylene glycol, polypropylene glycol, polyethylene-polypropylene (block and / or random) glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and / or random) glycol, poly Tetramethylene-propylene (block and / or random) glycols, polyhexamethylene ether glycols, polyoctamethylene ether glycols and mixtures of two or more thereof.

The polyester diol is a condensed polyester diol obtained by reacting a low molecular diol and / or a polyether diol having a molecular weight of 1000 or less with a dicarboxylic acid,
It includes polylactone diol obtained by ring-opening polymerization of lactone. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octamethylenediol, alkyl Dialkanolamines; low molecular weight diols having a cyclic group [for example, those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, m- and p-xylylene glycol, bis (hydroxyethylbenzene, 1,4-bis) (2-hydroxyethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) -diphenylpropane (ethylene oxide adduct of bisphenol A), and the like, and mixtures of two or more thereof. As the polyether diol, the above-mentioned polyether Examples thereof include polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, triethylene glycol, and mixtures of two or more thereof, and examples of the dicarboxylic acid include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, Glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and mixtures of two or more thereof;
Examples of the lactone include ε-caprolactone.

Polyester diols can be prepared by a conventional method, for example, by using a low molecular weight diol and / or a polyether diol having a molecular weight of 1,000 or less, a dicarboxylic acid or an ester-forming derivative thereof [eg, an anhydride (maleic anhydride, phthalic anhydride, etc.), a lower ester (terephthalate Acid dimethyl etc.), halide etc.] or its anhydride and alkylene oxide (eg ethylene oxide and / or propylene oxide) are reacted (condensed), or an initiator (low molecular diol and / or polyether having a molecular weight of 1000 or less) It can be produced by adding a lactone to a diol and a polyester diol.

Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylene adipate. Ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, polycarbonate diol; and mixtures of two or more thereof.

Average molecular weight of polymer diols such as polyether diol and polyester diol (by hydroxyl group measurement)
Is usually 500 to 5000, preferably 700 to 4000.

A low molecular weight diol can be used together with the polyether diol and the polyester diol.

Examples of the low-molecular diol include the low-molecular glycol described in the section of polyether diol, the low-molecular diol having a cyclic group, and the glycol ester of monohydroxymonocarboxylic acid (for example, those described in JP-A-61-190717). can give.

The molecular weight of these low molecular weight diols is usually from 62 to less than 500.

(A) and (a ') may be the same or different, but the same one is preferable.

The polyisocyanate (b) used in the present invention,
(B ') has 2 to 1 carbon atoms (excluding carbon in NCO group)
2 aliphatic polyisocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 12 carbon atoms, aromatic polyisocyanates having 6 to 20 carbon atoms, and modified products of these polyisocyanates ( Carbodiimide group, uretdione group, uretoimine group, urea group, buret group and / or isocyanurate group-containing modified product) can be used. Such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,1
1-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate,
2,6-diisocyanate methyl caproate, bis (2
-Isocyanate ethyl) fumarate, bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexyl Cilen diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate;
Xylylene diisocyanate, diethylbenzene diisocyanate; water-modified HDI, trimerized IPDI, etc .; tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified MDI (carbodiimide) Modified MDI), naphthylene diisocyanate; and mixtures of two or more thereof. Among these, preferred are aliphatic diisocyanates, cycloaliphatic diisocyanates and aromatic polyisocyanates in terms of resistance to cracking of the coating film, and particularly preferred are hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and It is diphenylmethane diisocyanate.

Although (b) and (b ') may be different, the same one is preferable.

In the present invention, the active hydrogen-containing compound (c) having a functional group selected from the group consisting of (c ₁ ), (c ₂ ) and (c ₃ ) is represented by the general formula (X) _m —Z— (Y) _n (1) [wherein, X is OH, NH, NH ₂ or SH; Z is an organic group; Y is COOX, SO ₃ X, or PO (OX) ₂ (X is H, a metal salt,
NH ₄ or amine cation); m is 1 or 2; n is an integer of 1 or more].

Specific examples of the active hydrogen compound (c ₁ ) having COOX include HOCH ₂ COOX HOCH (COOX) ₂ (HOCO ₂ ) C (CH ₃ ) COOX (HOCH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ COOX And derivatives thereof (polyether polyols, polyester polyols or polyurethane prepolymers containing these salts, such as a reaction product with propylene oxide, a reaction product with caprolactone or a reaction product with polyisocyanate).

The active hydrogen compound (c ₂ ) having SO ₃ X includes (HOCH ₂ ) ₂ C (CH ₃ ) SO ₃ XH ₂ NCH ₂ SO ₃ X HOCH ₂ CH ₂ SO ₃ X (HOCH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ SO ₃ X (HOCH ₂ CH ₂ OCO) ₂ C ₆ H ₃ SO ₃ X and its derivatives (polyether polyols, polyester polyols or polyurethane prepolymers containing these salts, such as reaction products with propylene oxide) , A reaction product with caprolactone or a reaction product with polyisocyanate).

Examples of the active hydrogen compound (c ₃ ) having PO (OX) ₂ include (HOCH ₂ ) ₂ C (CH ₃ ) PO (OX) ₂ (HOCH ₂ CH ₂ OCO) ₂ C ₆ H ₃ PO (OX) ₂ And derivatives thereof (polyether polyols, polyester polyols or polyurethane prepolymers containing these salts, such as a reaction product with propylene oxide, a reaction product with caprolactone or a reaction product with polyisocyanate).

Of these, preferred are dimethylolpropionic acid, phthalic acid glycol diester sulfonic acid, bishydroxyethylaminoethanesulfonic acid and bishydroxyethylaminoethanephosphoric acid, or metal salts, ammonium salts or amine cations of these acids. is there.

As a metal forming a salt, an alkali metal (lithium,
Examples thereof include sodium, potassium and the like) alkaline earth metals (calcium, barium, etc.) and the like.

Of these, preferred are sodium and potassium.

As amines forming amine cations, alkylamines (monomethylamine, triethylamine, etc.), alkanolamines (diethanolamine, triethanolamine, etc.), heterocyclic amines (piperidine, morpholine, piperazine, etc.) and aromatic amines (aniline, etc.)
Etc.

Of these, preferred are triethylamine and trimethylamine.

Examples of the long-chain active hydrogen-containing aliphatic hydrocarbon derivative used in the present invention include 1,2 and / or 1,4 polybutadiene modified with terminal hydroxyl groups or carboxyl groups, and hydrogenated 1,2 and / or 1,4 Examples thereof include a modified terminal hydroxyl group or carboxyl group of polybutadiene and a mixture thereof, and a modified terminal hydroxyl group or carboxyl of polyisobutylene and polychloroprene. Among these, polybutadiene derivatives having a molecular weight of 2000 or more are preferable from the viewpoint of dispersion effect, and particularly preferable are hydrogenated polybutadiene derivatives.

Non-polar solvents used in the present invention include aliphatic, alicyclic, and aromatic hydrocarbons.

Examples of aliphatic and alicyclic hydrocarbons include n-hexane,
N-heptane, n-octane, isooctane, petroleum benzine, ligroin, mineral spirits, cyclohexane, kerosene, petroleum naphtha and the like, and aromatic hydrocarbons include, for example, toluene, xylene, ethylbenzene and isopropylbenzene. Of these, aliphatic and alicyclic hydrocarbons are preferable from the viewpoint of stability of the dispersion.

The method for producing the urethane polymer (I) is [(a) +
Examples of the method include a method in which (c)] and (b) are collectively charged into a reaction vessel and a reaction is performed, and a method in which [(a) + (c)] and (b) are divided and a multistage reaction is performed.

In the polyol, (c) is usually 0.1 to 70 equivalent%, preferably 0.1 to 60 equivalent%. When the amount of (c) is less than 0.1 equivalent%, the dispersibility in the magnetic powder is insufficient, and when it exceeds 60 equivalent%, the viscosity of the magnetic coating material remarkably increases and the coatability deteriorates. In addition, (c ₁ ), (c ₂ ) and (c ₃ ) can be used in an optional ratio in combination.

When reacting [(a) + (c)] with (b),
The equivalent ratio of (b) and [(a) + (C)] is usually 0.6 to 1.5,
It is preferably 0.8 to 1.2. Equivalent ratio is less than 0.6 and
If it exceeds 1.5, the molecular weight of the polyurethane resin obtained by the reaction of [(a) + (c) and (b) will be low and the dispersibility will be lowered, and the abrasion resistance, scratch resistance and water resistance of the magnetic recording material will be decreased. Degradability tends to decrease.

The number average molecular weight of (I) is usually 3,000 to 200,000, preferably 5,000 to 150,000.

The molecular weight per functional group of (I) is usually 1,000 to 200,00.
It is 0, preferably 5,000 to 150,000. If the molecular weight per functional group is less than 1,000, the hydrolysis resistance will decrease.

In the present invention, the polyol (a ') as the dispersion stabilizer
And urethane polymers from polyisocyanates (b ') and long-chain active hydrogen-containing aliphatic hydrocarbon derivatives (II)
In preparing the composition, the ratio of the polyol (a ') and the active hydrogen-containing polybutadiene derivative [polyol (a') / active hydrogen-containing polybutadiene derivative (equivalent ratio) is usually 1 to 0.3] and the polyisocyanate (b ') is NCO. / Active hydrogen (equivalent ratio) is usually 1.2 to 0.8, preferably 1.1 to 0.9.

In the production of (I) and (II) in the present invention, the reaction temperature may be the same as the temperature usually adopted in carrying out urethanization in the industry, and if a solvent is used, it is usually 20 ° C to 10 ° C.
0 ℃, usually 20 ℃ ~ 220 ℃, when not using a solvent,
It is preferably 150 ° C to 200 ° C. In order to accelerate the reaction, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) used in ordinary urethane reactions may be used. . Further, if necessary, a polymerization terminator such as monohydric alcohol (methanol, butanol, cyclohexanol, etc.), monovalent amine (methylamine, dimethylamine,
Butylamine, dichlorohexylamine, etc.) and the like can also be used.

In the production of the urethane polymer and the dispersion stabilizer in the present invention, the reaction apparatus can be a production apparatus generally adopted in the relevant industry.

The amount of the urethane polymer (I) in the present invention is usually based on the total weight of the urethane polymer (I) and the nonpolar solvent.
It is 30 to 60%, preferably 35 to 55%.

The amount of urethane polymer (II) is urethane polymer (I)
It is usually 0.1 to 20%, preferably 0.5 to 15%, by weight.

In the production of the powdery polyurethane resin in the present invention, the polyol (a) and the polyisocyanate (b) and the active hydrogen-containing compound (c) having a functional group are dispersed in the presence of the dispersion stabilizer of the present invention dissolved in a nonpolar solvent. It is obtained by polymerizing a non-aqueous dispersion and removing the non-polar solvent by a known method such as filtration, centrifugation or decantation. After separation, the powder can be dried on a tray, on a wire mesh, or on a fluidized bed.

In the production of the non-aqueous dispersion, the amount of the dispersion stabilizer becomes large and the particle size becomes fine, while the amount of the dispersion stabilizer becomes small, the particle size becomes coarse. The lack of dispersion stabilizer can be compensated by increasing the stirring.

If necessary, the powdery polyurethane resin of the present invention may contain an auxiliary compounding agent. For example, coloring agents such as dyes and pigments for decorative coloring, inorganic fillers such as calcium carbonate, silica and glass fibers, organic modifiers such as AS resin, light resistance and heat deterioration Various stabilizers, softeners, plasticizers, and isocyanate-based crosslinking agents for improving strength, such as trimethylolpropane 1
Examples thereof include adducts synthesized from 3 mol of 1,6-hexamethylene diisocyanate, tolylene diisocyanate or 3 mol of isophorone diisocyanate.

[Examples] The present invention is further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.

Reference Example 1 (Example of synthesizing urethane polymer as dispersion stabilizer) 600 parts of toluene, 236.5 parts of polycaprolactone diol having a molecular weight of 2000 and 236.5 parts of a hydrogenation port having a molecular weight of 2000 are placed in a three-necked flask having a stirrer, a reflux condenser and a nitrogen blowing tube. 118.2 parts of butadiene polyol and 45.3 parts of isophorone diisocyanate were charged and heated at 100 ° C. and reacted for 6 hours to obtain a urethane polymer having a molecular weight of about 13000, a solid content of 40% and a viscosity of 2400 cps / 25 ° C. (this is referred to as S-1) ).

Example 1 600 parts of n-heptane and 10 parts of the stabilizer S-1 of Reference Example 1 were charged and dissolved in a four-necked flask having a stirrer, a reflux condenser, a nitrogen blowing tube, and a dropping roll. Then, with stirring, polycaprolactone diol 180 having a molecular weight of 2000
Parts, 90 parts of polytetramethylene ether glycol having a molecular weight of 1000, 32 parts of 1,4-ptanediol, 1 part of dimethylolpropionic acid and 97 parts of tolylene diisocyanate were added dropwise and dispersed. Further, react at 70 ℃ for 20 hours, particle size 10
A non-aqueous dispersion of ˜150 μm, solid content 40% was obtained. This was filtered through a 200-mesh wire net and dried for 1 hour in a circulating air dryer at 50 ° C to obtain a powdery polyurethane resin composition of the present invention having a particle size of 50 to 250 µ.

Example 2 In the same manner as in Example 1 except that 1.5 parts of N (C ₂ H ₅ ) ₃ cation of dimethylolpropionic acid was used instead of dimethylolpropionic acid in Example 1, the particle diameter was 10 to 150 μm, and the solid content was 4
A 0% non-aqueous dispersion was obtained. This is filtered through a 200-mesh wire net and dried for 1 hour in a circulating air dryer at 50 ° C to a particle size of 50-250
μ of the powdery polyurethane resin composition of the present invention was obtained.

Example 3 Instead of the dimethylolpropionic acid of Example 1, (HOCH
₂ ) A non-aqueous dispersion having a particle size of 10 to 150 μ and a solid content of 40% was obtained in the same manner as in Example 1 using 1.5 parts of ₂ C (CH ₃ ) SO ₃ Na.
This was filtered through a 200-mesh wire net and dried for 1 hour in a circulating air dryer at 50 ° C to obtain a powdery polyurethane resin composition of the present invention having a particle size of 50 to 250 µ.

Comparative Example 1 Reaction was initiated in the same manner as in Example 1 except that an acrylic polymer having a molecular weight of about 10,000 (butyl acrylate / methacrylate copolymer; copolymerization ratio = 85/15) was used as a stabilizer in Example 1. After 2 hours, the particles aggregated and became sticky.

[Effects of the Invention] The polyurethane resin composition and the method for producing the same according to the present invention have the following effects.

1. It has dispersion stability and is capable of producing powdery polyurethane resin.

2. The composition of the present invention has excellent dispersibility in magnetic powder.

In particular, the composition of the present invention has the above effects,
For example, audio tape, video tape, computer tape, data recorder tape, video sheet,
It is useful as a binder and a magnetic recording material for magnetic recording materials for metal tapes, metal disks and magnetic cards.

Claims (4)

[Claims] 1. An active hydrogen-containing compound (c) having a functional group selected from the group consisting of a polyol (a), a polyisocyanate (b) and the following (c ₁ ), (c ₂ ), (c ₃ ). A urethane polymer (I) from (1), a polyol (a ') as a dispersion stabilizer, a polyisocyanate (b') and a long-chain active hydrogen-containing aliphatic hydrocarbon derivative (II). And a polyurethane resin composition. _{(C 1) -COOX (c 2} ) -SO 3 X (c 3) -PO (OX) 2 X = H, metal salt, NH ₄ or amine cation 2. The composition according to claim 1, wherein the long-chain active hydrogen-containing aliphatic hydrocarbon derivative is an active hydrogen-containing polybutadiene derivative. 3. The composition according to claim 1, which is in a powder form. 4. A polyol (a), a polyisocyanate (b) and an active hydrogen-containing compound (c) having a functional group in a non-polar solvent in the presence of the dispersion stabilizer according to claim 1.
And a non-polar solvent are separated to produce a powdery polyurethane resin.