JPH09263623A - Polyurethane resin containing poly(ethylene-butylene) copolymer containing hydroxyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyurethane resin containing a specific recurring unit, having a single molecular weight distribution and excellent durability and flexibility and useful for adhesive, coating material, etc., by reacting a specific compound containing active hydrogen group with an organic diisocyanate. SOLUTION: The objective polyurethane resin containing the recurring units of formulas IV and V (X to Z are each a residue derived from the main body of each group) and having a number-average molecular weight of 5,000-500,000 is produced by reacting (A) a compound containing active hydrogen group with (B) an organic diisocyanate such as 4,4'-diphenylmethane diisocyanate. The compound containing active hydrogen group is a hydroxyl-containing random or block poly(ethylene-butylene) copolymer having a molar ratio of the hydroxyl-containing poly(ethylene-butylene) copolymer of formulas I to III to the other compound containing active hydrogen group (a/b in formulas IV and V) of 1/99 to 100/0 and an ethylene/butylene molar ratio (m/n in formulas I to III) of 10/90 to 90/10 in the hydroxyl-containing poly(ethylene-butylene) copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydroxyl group-containing poly (ethylene-butylene) copolymer-containing polyurethane resin, and more particularly to a hydroxyl group-containing poly (ethylene-butylene) copolymer-containing polyurethane resin having excellent physical properties.

[0002]

Polyurethane resins are generally obtained by reacting active hydrogen group-containing compounds, for example, polyols such as polyester polyols, polyether polyols, polycarbonate polyols, polyamines, and active methylene compounds with organic polyisocyanates. On the other hand, a polyurethane resin obtained by reacting a hydroxyl group-containing high molecular weight hydrocarbon with a polyisocyanate compound is used for a special purpose as an adhesive for various plastic films and the like. As an application example of a conventional hydroxyl group-containing high-molecular-weight hydrocarbon-containing polyurethane resin, a reactive hot melt adhesive using a polydiene-based hydrocarbon compound-containing polyurethane resin (JP-A-3-207782) and a polyisoprene-containing polyurethane resin are used. A resin composition for printing ink (Japanese Patent Laid-Open No. 5-209146) has been disclosed.

[0003]

However, since the polyolefin-containing polyurethane resin obtained by this method has a double bond and the hydroxyl group-containing polyolefin has too many functional groups, the molecular weight of the polyurethane resin is not sufficient. There was a problem in durability without increasing the size.

[0004]

In view of the above circumstances, the inventors of the present invention have made extensive studies on the introduction of polyolefin into a polyurethane resin, and as a result, completed the present invention.

That is, the present invention provides a polyurethane containing a hydroxyl group-containing poly (ethylene-butylene) copolymer having a repeating unit represented by the following general formula (1) obtained by reacting an active hydrogen group-containing compound with an organic diisocyanate. The resin is a hydroxyl group-containing poly (ethylene-butylene) copolymer (2), (3), and / or an active hydrogen group-containing compound represented by the following general formulas (2), (3) and (4).
Alternatively, in the polyurethane resin in which the molar ratio of (4) to another active hydrogen group-containing compound (a / b in the general formula (1)) is 1/99 to 100/0, a hydroxyl group-containing poly (ethylene-butylene) is used. ) The copolymer is a random copolymer or a block copolymer, and the molar ratio of ethylene / butylene in the hydroxyl group-containing poly (ethylene-butylene) copolymer [of the general formulas (2), (3) and (4)] m / n] is 10/9
It is 0-90 / 10 and the number average molecular weight of this polyurethane resin is 5,000-500000, It is a hydroxyl-containing poly (ethylene-butylene) copolymer containing polyurethane resin.

[0006]

(Wherein X represents a residue obtained by removing an isocyanate group from an organic diisocyanate, Y represents a residue obtained by removing an OH group from a hydroxyl group-containing poly (ethylene-butylene) copolymer, and Z represents an active group. Represents a residue obtained by removing an active hydrogen group from a hydrogen group-containing compound.)

[0007]

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[0008]

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[0009]

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[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. The hydroxyl group-containing poly (ethylene-butylene) copolymer used in the present invention is a poly (ethylene-butylene) copolymer obtained by living polymerization such as radical polymerization or anionic polymerization of ethylene and butylene, and a vinyl alcohol compound. Can be obtained by grafting or by treating the terminal polymerization initiator component.

The amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer introduced into the polyurethane resin of the present invention is 1 to 100 mol% based on the active hydrogen group-containing compound.

The hydroxyl group-containing poly (ethylene-butylene) copolymer used in the present invention has a molar ratio of ethylene to butylene of 10/90 to 90/10. When the molar ratio of ethylene to butylene is greater than 10/90, or when the molar ratio of ethylene to butylene is greater than 90/10, the crystallinity is high and the melting temperature is high. The target polyurethane resin cannot be obtained because the solubility of the compound in a solvent decreases.

The number average molecular weight of the hydroxyl group-containing poly (ethylene-butylene) copolymer is 500 to 10,000,
The preferred number average molecular weight is 1000 to 9000. When the number average molecular weight of the hydroxyl group-containing poly (ethylene-butylene) copolymer is less than 500, the poly (ethylene-butylene) chain introduced into the polyurethane resin is too short,
Only the effect of introducing an aliphatic glycol will be achieved. Further, when the number average molecular weight is 10,000 or more, the hydroxyl group-containing poly (ethylene-butylene) copolymer has low compatibility with other polyols and isocyanates, and also has a hydroxyl group-containing poly (ethylene-butylene) copolymer. Since the viscosity is high, the melting temperature is high depending on the molecular weight, and the solubility in a solvent is low, the target polyurethane resin cannot be obtained.

The hydroxyl group content of the hydroxyl group-containing poly (ethylene-butylene) copolymer is 0.5 to 3.0 per molecule.
The number is preferable, and 0.8 to 2.0 is particularly preferable. When the number of hydroxyl groups is less than 0.5, the hydroxyl group-containing poly (ethylene-butylene) copolymer is hardly introduced into the polyurethane resin and is in a free state. As a result,
Since the hydroxyl group-containing poly (ethylene-butylene) copolymer is separated, the storage stability becomes poor. When the number of the hydroxyl groups is 3.0 or more, the resin cannot be obtained due to gelation depending on the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer introduced during the synthesis of the polyurethane resin.

Specific examples of the hydroxyl group-containing poly (ethylene-butylene) copolymer include HPM- of Kraton Liquid ^TM series of Shell Japan Co., Ltd.
1202 and HPVM-2202.

The organic diisocyanates used in the present invention include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethyl xylylene diisocyanate,
2-methylpentane-1,5-diisocyanate, 3-
Methyl pentane-1,5-diisocyanate, 2,2
4-trimethylhexahexylene-1,6-diisocyanate, 2,4,4-trimethylhexahexylene-1,6
-Aliphatic and alicyclic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4'-diphenylmethane diisocyanate, 4,
4'-diphenyldimethylmethane diisocyanate,
Aromatic diisocyanates such as 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, orthoxylylene diisocyanate, metaxylylene diisocyanate There are non-yellowing diisocyanates such as isocyanate, para-xylylene diisocyanate and tetramethyl xylylene diisocyanate, and mixtures thereof.

As the active hydrogen group-containing compound which can be used in the present invention, the above-mentioned hydroxyl group-containing poly (ethylene-
All but the butylene) copolymer can be used. Specific examples include polyester polyols, polyether polyols, polycarbonate polyols, acrylic polyols, polymer polyols such as polyolefin polyols, polyether polyamines, low molecular weight polyols used as chain extenders, low molecular weight polyamines, and low molecular weight amino alcohols. . Also, monoalcohol,
A reaction terminator such as monoamine or monoisocyanate can also be used. The active hydrogen group-containing compound can be used alone or in combination of two or more. In addition, these active hydrogen group-containing compounds may contain a carboxyl group, a tertiary amino group, a sulfonic acid group, a phosphoric acid group and the like, and salts thereof.

Specific examples of the polyester polyol, which is a polymer polyol that can be used in combination in the present invention, include ethylene glycol, 1,2-propanediol, and 1,3.
-Propanediol, 1,2-butanediol, 1,3
-Butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-
Pentanediol, 1,4-pentanediol, 1,5
-Pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,
6-hexanediol, 2,2,4-trimethyl-1,
3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, ethylene of bisphenol A Low molecular weight glycols such as oxide adducts, propylene oxide adducts of bisphenol A, and succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylene diene Examples thereof include polyesters having hydroxyl groups at both terminals obtained by dehydration condensation reaction with a dicarboxylic acid such as carboxylic acid, and polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone. Specific examples of the polyether polyol include epoxides such as ethylene oxide and propylene oxide, which may be used alone or as a mixture, and water, ethylene glycol, dipropylene ether glycol, 1,4-
A polyether polyol obtained by using butanediol, neopentylene glycol or the like as an initiator for ring-opening polymerization, and
Examples thereof include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran. Specific examples of the polycarbonate polyol include those obtained by the deethanoling reaction of the low molecular weight polyol used in the above polyester polyol and ethylene carbonate, and the dephenoling reaction of the low molecular weight polyol and diphenyl carbonate. Other polymer polyols include acrylic polyol, hydroxyl group-containing polybutadiene,
Examples thereof include hydroxyl group-containing hydrogenated polybutadiene and hydroxyl group-containing polyisoprene. In addition, trifunctional alcohols such as glycerin and trimethylolpropane, and trifunctional acid such as trimellitic acid are included in the constituent components of the hydroxyl group-containing polymer polyol.
It may contain functional carboxylic acids.

A chain extender can be used in the present invention. As the chain extender, organic diamine and glycol are used, and as the organic diamine, ethylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexyldiamine, 4,4'-methylenebis (cyclohexanamine), hydrazine and the like, and these A mixture of As glycols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2- Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-
Methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol,
2,2-diethyl-1,3-propanediol, 2-n
-Butyl-2-ethyl-1,3-propanediol, ethylene oxide and propylene oxide adducts of bisphenol A, ethylene oxide and propylene oxide adducts of aniline, and the like. Trifunctional alcohols such as glycerin and trimethylolpropane can also be used within the range where gelation does not occur.

In the present invention, a reaction terminator may be used. Examples of the reaction terminator include monoalcohol, monoamine, amino alcohol and the like. Specific monoalcohols include methanol, ethanol, propanol, isopropanol, 2-ethylhexanol and the like. Examples of monoamines include primary amines such as ethylamine, propylamine and butylamine, and secondary amines such as diethylamine and dibutylamine. Examples of amino alcohols include monoethanolamine and diethanolamine.

A urethanization catalyst can be used as a reaction catalyst when synthesizing the polyurethane resin in the present invention. Specific examples thereof include organic metal compounds such as dibutyltin dilaurate (hereinafter abbreviated as DBTDL), organic amines such as triethylenediamine, and salts thereof.

The method for producing the polyurethane resin of the present invention comprises:
It can be synthesized by any of bulk polymerization, solution polymerization and non-aqueous emulsion polymerization. Further, a hydroxyl group-containing poly (ethylene-butylene) and another active hydrogen compound are mixed in advance, and a one-shot method in which this mixture is reacted with an organic diisocyanate, or a hydroxyl group-containing poly (ethylene-butylene) and an organic compound are first mixed. Diisocyanate is reacted in advance and then other active hydrogen compound is reacted, or other active hydrogen compound and organic diisocyanate are reacted in advance and then hydroxyl group-containing poly (ethylene-butylene) is reacted. It can also be synthesized by the prepolymer method.

When a solvent is used, an aromatic solvent such as toluene and xylene, an aliphatic solvent such as hexane, an ester solvent such as ethyl acetate and butyl acetate, a ketone solvent such as acetone and methyl ethyl ketone, diethyl ether and the like. Ether solvent, methanol, ethanol, alcohol solvent such as isopropanol, chloroform, methylene chloride, halogen solvent such as trichloroethane, ethylene glycol monomethyl ether, cellosolve solvent such as ethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, Dimethylformamide,
Examples thereof include dimethylacetamide. The above compounds may be used alone or in combination of two or more.

The number average molecular weight of the polyurethane resin thus obtained is preferably 5,000 to 500,000,
More preferably, it is in the range of 10,000 to 200,000. When the number average molecular weight of the polyurethane resin is less than 5,000, mechanical strength is not exhibited. Also, 500000
With the above, workability becomes poor.

The obtained polyurethane resin can be used as a one-pack type. Also, it can be used as a two-part type to which a crosslinking agent (curing agent) is added. Further, the obtained polyurethane resin may be used alone, or may be used by adding other resin such as polyvinyl chloride, nylon, polyester resin and acrylic resin.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A 2-liter four-necked flask equipped with a stirrer, a thermometer, an Arene condenser, and a nitrogen gas inlet tube was used to obtain the ethanol-free reaction of 1,6-hexanediol and ethylene carbonate. 504 g of a polycarbonate diol (HG-PCD-2000) with hydroxyl groups at both ends having a number average molecular weight of 2000, 30 g of a hydroxyl group-containing poly (ethylene-butylene) copolymer (trade name: HPVM-2202 Shell Japan KK), and toluene 700 g was charged and stirred uniformly. 64 parts of 4,4'-diphenylmethane diisocyanate (4,4'-MDI) was added to this polyol solution.
g, 0.08 g of DBTDL was charged, and NCO was added at 80 ° C.
The reaction was allowed to proceed until the group disappeared. After confirming disappearance of the NCO group by IR, 700 g of methyl ethyl ketone was charged and uniformly stirred to obtain a polyurethane resin solution PU-1. PU-1 has a solid content of 30% and a viscosity of 6000 cP
(25 ° C). These are summarized in Table 1.

Example 2 An apparatus similar to that of Example 1 was used, except that the number average molecular weight of 3000
Polyester diol containing hydroxyl groups at both ends obtained by dehydration condensation of methyl-1,5-pentanediol and adipic acid (trade name: Clapol P-3010, manufactured by Kuraray)
391 g, HPVM-2202 120 g, and toluene 200 g were charged and uniformly stirred. Isophorone diisocyanate (IPDI) was added to this polyol solution 67
g and 0.08 g of DBTDL were charged and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing NCO groups at both ends. To this prepolymer solution, add 50 parts of toluene.
After 0 g and 420 g of methyl ethyl ketone were added and homogenized, a mixed solution of 280 g of isopropanol, 21 g of isophoronediamine and 1 g of monoethanolamine was added all at once, and the mixture was reacted at 40 ° C. until the NCO group disappeared, and the polyurethane resin solution PU- Got 2. PU-2 had a solid content of 30% and a viscosity of 2500 cP (25 ° C). These are summarized in Table 1.

Example 3 A device similar to that of Example 1 was charged with a poly (ethylene-containing hydroxyl group).
Butylene) copolymer (trade name: HPVM-1202, Shell Japan Co., Ltd.) was dissolved in 60 g and toluene in 700 g. To this solution, 130 g of 2,4-tolylene diisocyanate (2,4-TDI) and DBTDL of 0.
08 g was charged and reacted at 80 ° C. for 4 hours. Poly (oxypropylene) glycol (PPG-1000) 37 containing hydroxyl groups at both ends and having a number average molecular weight of 1000 was added to this solution.
1 g and neopentyl glycol (NPG) 39 g were charged and further reacted at 80 ° C. until the NCO group disappeared. After confirming disappearance of the NCO group by IR, 700 g of methyl ethyl ketone was charged and uniformly stirred to obtain a polyurethane resin solution PU-3. PU-3 had a solid content of 30% and a viscosity of 2300 cP (25 ° C). These are summarized in Table 1.

COMPARATIVE EXAMPLE In the same apparatus as in Example 1, 3 pieces of Clapol P-3010 were used.
91 g, hydroxyl group-containing polybutadiene (trade name: Poly
bd R-45HT, manufactured by Idemitsu Petrochemical), 120 g,
200 g of toluene was charged and stirred uniformly. 67g of IPDI and 0.08 of DBTDL were added to this polyol solution.
g, and reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer solution containing NCO groups at both ends. To this prepolymer solution was added 500 g of toluene and 4 parts of methyl ethyl ketone.
After adding 20 g and homogenizing, further isopropanol 280
When a mixed solution of g, 21 g of isophoronediamine and 1 g of monoethanolamine was added all at once, gelation occurred.
These are summarized in Table 1.

[0031]

[Table 1]

[Measurement of Physical Properties of Polyurethane Resin] Preparation of Test Pieces PU-1 to PU-3 were cast to dryness to 100 μm, and then cured at 60 ° C. × 30 minutes + 100 ° C. × 30 minutes to obtain the following physical properties. A sample for measurement was prepared. (1) Tensile properties The obtained film was punched out with a No. 4 dumbbell cutter specified in JIS K-6301, and Tensilon UTM-50 was used.
0 (manufactured by Orientec), tensile speed: 200 mm /
The tensile properties of the film were measured at a temperature of 25 ° C. and a humidity of 50%. (2) Dynamic viscoelasticity The obtained film was punched out into a size of 4 mm × 50 mm, and a frequency was measured with a rheovibron (manufactured by Orientec Co., Ltd.).
The dynamic viscoelasticity was measured under the conditions of 35 Hz and heating rate: 2 ° C./min. The glass transition point (Tg) was the temperature at which E ″ (loss modulus) was maximized. (3) Softening point The obtained film was punched out with a No. 2 dumbbell cutter specified in JIS K-6301 and tested. 500gf / c on one side
A softening point was defined as a temperature at which the film elongation was tripled at a temperature rising rate of 5 ° C./min by applying a load of m ² . (4) Molecular Weight The obtained film was dissolved in toluene-containing tetrahydrofuran as a standard to a concentration of about 1%,
The molecular weight was measured by HLC-8020 manufactured by Tosoh Corporation. The polystyrene calibration curve was used as the molecular weight calibration curve. Table 2
Strength at break, elongation at break, Tg and E'at 25 ° C
The measurement results of (dynamic elastic modulus), softening point and molecular weight are shown.

[0033]

[Table 2]

Analytical Chemistry Vol.41
Corish was decomposed according to the method of P.655-658 (1992), and the decomposed product was analyzed. The mixture after decomposition was treated with GPC-IR, ¹ H
-NMR and ¹³ C-NMR were analyzed. The results are shown in Table 3.

[0035]

[Table 3]

The resin components of PU-1 to 3 were analyzed by FT-IR. The results are shown in Table 4.

[Table 4]

[0037]

As described above, according to the present invention, a hydroxyl group-containing poly (ethylene-butylene) copolymer-containing polyurethane resin having excellent physical properties and a single molecular weight distribution can be obtained. The polyurethane resin of the present invention can be applied to the fields of adhesives, paints, printing inks, magnetic recording media, fibers, elastomers, flexibility imparting agents, impact resistance improvers and the like.

[Brief description of drawings]

FIG. 1 shows the polyurethane resin obtained in Example 1 (PU
It is a GPC chart of -1).

FIG. 2 shows the polyurethane resin obtained in Example 1 (PU
It is an FT-IR chart of -1).

FIG. 3 shows the polyurethane resin obtained in Example 1 (PU
It is a < ¹ > H-NMR chart of -1).

FIG. 4 shows the polyurethane resin obtained in Example 1 (PU
It is a ¹³ C-NMR chart of -1).

Claims (1)

[Claims] 1. A polyurethane resin containing a hydroxyl group-containing poly (ethylene-butylene) copolymer having a repeating unit represented by the following general formula (1), which is obtained by reacting an active hydrogen group-containing compound with an organic diisocyanate. As the active hydrogen group-containing compound, the following general formula (2),
Hydroxyl group-containing poly (ethylene-butylene) copolymer (2), (3) and / or represented by (3) and (4)
In the polyurethane resin in which the molar ratio (a / b in the general formula (1)) of (4) and another active hydrogen group-containing compound is 1/99 to 100/0, a hydroxyl group-containing poly (ethylene-butylene) copolymer is used. The polymer is a random copolymer or a block copolymer, and hydroxyl group-containing poly (ethylene-butylene)
The ethylene / butylene molar ratio [m / n in the general formulas (2), (3) and (4)] in the copolymer is from 10/90 to 90.
/ 10 and the number average molecular weight of the polyurethane resin is 5
Polyurethane resin containing hydroxyl group-containing poly (ethylene-butylene) copolymer, characterized in that it is 000 to 500,000. Embedded image (In the formula, X represents a residue obtained by removing an isocyanate group from an organic diisocyanate, Y represents a residue obtained by removing an OH group from a hydroxyl group-containing poly (ethylene-butylene) copolymer,
Z represents a residue obtained by removing the active hydrogen group from the active hydrogen group-containing compound. ) Embedded image Embedded image