JPH10259302A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in light resistance and humidity resistance as well as water swellability and suitable for clothes and sanitary materials by mixing a hydrophilic polyurethane resin having active hydrogen atoms in the form of functional groups at the terminals and side chains with a polyisocyanate or aminoplast crosslinking agent. SOLUTION: A hydrophilic polyurethane resin having active hydrogen atoms in the form of functional groups at the terminals and side chains and obtained by reacting a monomer having two active hydrogen atoms in the molecule and a polyfunctional monomer having three active hydrogen atoms in the molecule with an organic diisocyanate is mixed with a polyisocyanate or aminoplast crosslinking agent. It is desirable that the monomer having two active hydrogen atoms is used in an amount of 5-70 mol% based on the amount of the monomer having two active hydrogen atoms. It is suitable that the crosslinking agent is used in an amount of 1-70 pts.wt. per 100 pts.wt. solid content of the hydrophilic polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having water swelling properties and capable of providing a film having excellent light resistance and moisture permeability. More specifically, the present invention relates to a hydrophilic polyurethane resin and a crosslinking agent. The present invention relates to a resin composition in which a hydrophilic polyurethane resin as a main material has a crosslinkable functional group coexisting at its terminal and a side chain.

[0002]

2. Description of the Related Art Heretofore, water-swellable resins include acrylic resins mainly composed of sodium polyacrylate, water-absorbing water-soluble resins such as polyvinyl alcohol, starch, and cellulose derivatives, and the use of these with other synthetic resins. Mixed resins can be mentioned, but all of these water-swellable resins have insufficient properties such as hardness, strength, elastic recovery and durability when formed into films.

[0003]

As for the water swellable resin, a polyurethane resin type is not crosslinked with a polyurethane resin mainly containing an ethylene oxide group such as polyethylene glycol, or a polyethylene glycol having a hydroxyl group at a terminal. There is a type that crosslinks polyisocyanate with a polyurethane resin mainly composed of an ethylene oxide group such as, but it is extremely difficult to achieve both water swelling and light resistance. It was only used for such limited applications.

[0004] The present invention solves the above-mentioned problems of the conventional water-swellable resin composition, and provides a resin composition which is excellent in water swellability, light resistance and moisture permeability. It is intended for.

[0005]

Means for Solving the Problems In order to achieve the above object, the present invention according to claim 1 of the present invention relates to a monomer having two active hydrogens in a molecule and a monomer having three active hydrogens in a molecule. A hydrophilic polyurethane resin having an active hydrogen as a functional group at a terminal and a side chain obtained by reacting an organic diisocyanate with a polyfunctional monomer having at least one polyfunctional monomer, and a water swelling property comprising a polyisocyanate or aminoplast crosslinking agent,
It is characterized by a resin composition having excellent light resistance and moisture permeability.

According to a second aspect of the present invention, there is provided a hydrophilic polyurethane resin having an active hydrogen as a functional group at a terminal and a side chain according to the first aspect of the present invention. It is characterized in that a polyfunctional monomer having three or more hydrogens is used in an amount of 5 to 70 mol% of a monomer having two active hydrogens in a molecule.

[0007] Further, the invention according to claim 3 is based on claim 1.
Alternatively, the crosslinked film using the resin composition obtained in 2 has a water swelling ratio of 50 to 300%.

[0008] In short, the present invention relates to a method for producing a hydrophilic polyurethane resin, which comprises, as a monomer to be reacted with an organic diisocyanate, a monomer having two active hydrogens in a molecule and three or more active hydrogens in a molecule. A polyurethane resin having active hydrogen as a functional group capable of binding to a cross-linking agent at both ends and side chains by using a polyfunctional monomer in combination. By reacting the active hydrogen with the polyisocyanate, a resin composition having a three-dimensional crosslinked structure excellent in water swelling, light resistance and moisture permeability can be obtained.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In order to satisfy the water swelling property, light resistance (light discoloration resistance and light deterioration) and moisture permeability which are the objectives of the present invention,
Needless to say that the cross-linking structure and cross-linking density of the hydrophilic polyurethane resin having active hydrogen at both the terminal and the side chain and the cross-linking agent are particularly important, but in order to make the water swelling performance sufficient, In producing the hydrophilic polyurethane resin, first, as a monomer having two active hydrogens in the molecule, a polyalkylene ether glycol having a large hydrophilicity and an average molecular weight of 400 to 4000 or a polyester polyol having a hydroxyl group at a terminal may be used. preferable.

Examples of such polyalkylene ether glycols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, glycerin propylene oxide adduct, polyether polyols having ethylene oxide added to the terminals, and polyether polyols grafted with vinyl monomers. There is also a polyester polyol having a hydroxyl group at the terminal, ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, alkylene glycols such as neopentyl glycol, and succinic acid, glutaric acid, adipic acid, Carboxylic acids such as sebacic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, etc. Good those obtained by reacting such. Further, poly-ε-caprolactone polyol, polycarbonate diol and the like can be used alone or as a mixture.

Next, in producing the hydrophilic polyurethane resin, a polyfunctional monomer having three or more active hydrogens in a molecule, which is used for giving active hydrogen as a functional group to a side chain, is used. Are polyhydric alcohols such as glycerin, petriol, trimethylolpropane, pentaerythritol, and triethanolamine; polyamines such as iminobispropylamine and triethylenetetramine; and alcohols and amines such as diethanolamine and aminoethylethanolamine. A monomer having three or more active hydrogens capable of reacting with an organic diisocyanate in the coexistence of an organic diisocyanate can be used alone or as a mixture.

As the organic diisocyanate, 2,4-
And 2,6-toluylene diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5
5'-trimethylcyclohexyl isocyanate, 2,
There are aliphatic diisocyanates such as 6-diisocyanate methylcaproate, and these may be used alone or as a mixture. However, when light discoloration resistance is particularly important among light resistance performances, it is preferable to use an aliphatic diisocyanate, and when using an aromatic diisocyanate, it is desirable to add a photodiscoloration inhibitor such as an ultraviolet absorber.

In the above-mentioned reaction between the monomer and the organic diisocyanate, if necessary, hydrazine, ethylenediamine, tetramethylenediamine, water, anhydrous piperazine, 3-aminomethyl-3 may be used as a hardness modifier and / or a chain extender. , 5,5'-Trimethylcyclohexylamine, ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol and the like can be used alone or in combination.

The hydrophilic polyurethane resin obtained as described above may be a modified polyurethane resin copolymerized with a monomer such as fluorine, amino acid or silicone, if necessary, or a mixture of these resins.

The hydrophilic polyurethane resin having an active hydrogen at the terminal and the side chain according to the present invention is blended with the above-mentioned elementary component so that an isocyanate group does not remain at the terminal and reacted to have an average molecular weight of 30,000 to 120,000.
In the formulation, the amount of the polyfunctional monomer having three or more active hydrogens in the molecule used for imparting active hydrogen to the side chain is as follows. 5 to 70 mol% of the amount of the monomer having two hydrogens
(Preferably 25 to 50 mol%).

This was obtained when the amount of the polyfunctional monomer having three or more active hydrogens in the molecule relative to the monomer having two active hydrogens in the molecule was less than 5 mol%. The active hydrogen in the side chain that reacts with the crosslinking agent in the resin solution is small, and it is difficult to achieve all of the water swelling property, light resistance and moisture permeability characteristic of the present invention. In addition, 70 mol%
If the amount is too large, the crosslink density of the obtained resin solution is too high, and there are difficulties in liquid stability, liquid viscosity, solubility in a solvent, and the like, and the water swellability is significantly reduced.

The organic solvent used to obtain a hydrophilic polyurethane resin from the above-mentioned components is methyl ethyl ketone (MEK), dimethylformamide (DMF), toluene, xylene, isopropyl alcohol, sec-
Butyl alcohol, tert-butyl alcohol, cyclohexanone, tetrahydrofuran, ethyl acetate and the like may be used alone or in combination.

In the present invention, a trivalent crosslinking agent used to obtain a hydrophilic polyurethane resin solution having a three-dimensionally crosslinked structure by binding to active hydrogen as a functional group on the terminal and side chain of the hydrophilic polyurethane resin includes: A polyisocyanate adduct composed of methylolpropane and diisocyanate, a polyisocyanurate obtained by modifying diisocyanate with isocyanurate, or a blocked isocyanate obtained by blocking these polyisocyanates with oximes or phenols, alone or in a mixture, is used. In addition to such polyisocyanates, aminoplasts such as methoxymethylolated melamine and methoxymethyl urea may be used as a crosslinking agent, and these may be used alone or in combination.

The amount of these crosslinking agents used is as follows:
If the amount is less than 1 part by weight based on 100 parts by weight of the solid content of the hydrophilic polyurethane resin having active hydrogen at the terminal and the side chain, the crosslinking density is small and the light resistance is not improved. 1 to 70 parts by weight (preferably 3 to 20 parts by weight) is appropriate because the water swelling property and the elasticity are impaired because it is too large.

In the present invention, the term "active hydrogen having a terminal or side chain of the hydrophilic polyurethane resin" means an active hydrogen capable of reacting with polyisocyanate or aminoplast, such as a hydroxyl group, a carboxyl group or an amino group. Have

By adding a crosslinking agent to a hydrophilic polyurethane resin having active hydrogen at the terminal and side chain obtained by the above-described elemental component and performing a crosslinking reaction, the hydrophilic polyurethane resin has good water swelling property, light resistance and moisture permeability. Although an excellent resin composition can be obtained, the water swelling property is desirably 50 to 300% (preferably 60 to 200%) as a water swelling ratio. If the water swelling ratio is larger than 300%, the light resistance is not good because the cross-linking density with respect to the length of the main chain is small even if the cross-linking reaction is performed at both the terminal and the side chain. If it is less than 50%, the water swelling characteristic of the present invention is insufficient.

The above-mentioned water swelling ratio is determined by applying the above resin composition onto release paper so that the thickness after curing becomes 40 μm, and drying it at 80 ° C. × 10 minutes and at 120 ° C. × 10 minutes. Aged at 60 ° C. for 96 hours to obtain a cured film,
After removing the release paper, a film cut into a square having a side of 5 cm was used as a sample. This sample film was immersed in pure water at 25 ° C. for 1 hour, taken out, and taken out of the length of each side swollen by immersion. The product was calculated as the area of the film after swelling according to the following equation (1).

[0023]

(Equation 1)

Since the resin composition of the present invention thus obtained has various properties such as water swelling property, light resistance and moisture permeability, it can be used for moisture-permeable clothing, gloves, sanitary materials, etc. It can be used as a primer for inkjet printing.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. All parts in the examples are parts by weight.

Example 1 200 parts of a polycarbonate diol having an average molecular weight of 2,000 having hydroxyl groups at both terminals, 800 parts of polyethylene glycol having the same average molecular weight of 2,000 and 59 parts of hexylene glycol were blended and uniformly mixed under a nitrogen stream. Then, the mixture was added to dicyclohexylmethane-
Add 524 parts of 4,4'-diisocyanate and add 110 ° C
For 3 hours, 1605 parts of DMF, MEK240
8 parts, and aminoethylethanolamine 52
And 85 parts of 3-aminomethyl-3,5,5'-trimethylcyclohexylamine to carry out a heating reaction, block the isocyanate residues in the reaction solution with monoethanolamine, and activate the terminal and side chains. A hydrophilic polyurethane resin solution having hydrogen was obtained. The viscosity of this solution is 30
% Concentration was 29000 cps / 30 ° C.

The hydrophilic polyurethane resin solution 1 obtained above
After uniformly mixing 30 parts of MEK and 3 parts of polyisocyanate (Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) composed of trimethylolpropane and diisocyanate in 00 parts, release the mixed solution into release paper (manufactured by Ajinomoto Co., DNTP-
NML) to give a dry film thickness of 40 μm.

Comparative Example 1 30 parts of MEK was mixed with 100 parts of the hydrophilic polyurethane resin solution having active hydrogen groups at the terminals and side chains obtained in Example 1, and 30 parts of MEK was mixed. .

Example 2 100 parts of ethylenediethylene adipate having an average molecular weight of 2,000 having hydroxyl groups at both ends, 1200 parts of polyethylene glycol having an average molecular weight of 4,000 having hydroxyl groups at both ends, and 58.5 parts of butylene glycol were blended. The mixture was mixed uniformly under a stream of air. Next, 444 parts of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate was added to the mixture, and the mixture was heated at 120 ° C. for 2.5 hours. Further DMF 1780
, 2670 parts of MEK, and 105 parts of diethanolamine, and heated. The solution was extracted and the viscosity was measured.
When the concentration reached 20,000 cps / 30 ° C. at a% concentration, isocyanate residues in the reaction solution were blocked by adding monoethanolamine to obtain a hydrophilic polyurethane resin solution having active hydrogen at the terminal and side chains.

The hydrophilic polyurethane resin solution 1 obtained above
30 parts of MEK and 00 parts of polyisocyanurate type polyisocyanate obtained by modifying diisocyanate with isocyanurate (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.)
After uniformly mixing the two parts, the mixed solution was coated on release paper so that the dry film thickness was 40 μm, to obtain a dry film.

Comparative Example 2 100 parts of ethylenediethylene adipate having an average molecular weight of 2,000 having hydroxyl groups at both ends, 1200 parts of polyethylene glycol having an average molecular weight of 4,000 having hydroxyl groups at both ends, and 58.5 parts of butylene glycol were blended. The mixture was uniformly mixed under an air stream. Next, 3-isocyanatomethyl-3,5,5'-
After adding 444 parts of trimethylcyclohexyl isocyanate and heating at 120 ° C. for 2.5 hours, DMF was further added.
1780 parts, 2670 parts of MEK, 86 parts of anhydrous piperazine were added and heated to 23,000 cps / 30 at 30% concentration.
When the viscosity reached ° C, the isocyanate residue in the reaction solution was blocked with monoethanolamine to obtain a hydrophilic polyurethane resin solution having active hydrogen at the terminal.

Using the hydrophilic polyurethane resin solution obtained above, a dry film was obtained in the same manner as in Example 2.

Example 3 1200 parts of polyethylene glycol having an average molecular weight of 3000 having hydroxyl groups at both ends, 106.2 parts of hexylene glycol, and 624 parts of DMF were blended and uniformly mixed under a nitrogen stream. Then, 150 parts of 4,4'-diphenylmethane diisocyanate was added to the mixture to give 70 parts.
Heated at ° C for 2 hours. Thereafter, after confirming that the isocyanate in the reaction solution has disappeared, 310.8 parts of 3-isocyanatomethyl-3,5,5′-trimethylcyclohexyl isocyanate was added, and the mixture was heated at 115 ° C. for 2 hours. Department, MEK2629
Parts, 9.2 parts glycerin, 3-aminomethyl-3,5,
102 parts of 5'-trimethylcyclohexylamine was added and heated to 30% concentration at 29000 cps / 30 ° C.
When the reaction reached, the isocyanate residue in the reaction solution was blocked with monoethanolamine to obtain a hydrophilic polyurethane resin solution having active hydrogen at the terminals and side chains.

The hydrophilic polyurethane resin solution 1 obtained above
30 parts of MEK, 00 parts of benzotriazole-based ultraviolet absorber (Tinuvin P, manufactured by Ciba-Geigy, Japan) 0.1 part,
5 parts of a modified methoxymethylolated melamine resin (Euramine T-21, manufactured by Mitsui Toatsu Chemicals, Inc.) and 0.1 part of P-toluenesulfonic acid were added and uniformly mixed. A dry film was obtained in the same manner.

Comparative Example 3 2400 parts of polyethylene glycol having an average molecular weight of 4000 having hydroxyl groups at both ends and 24.8 parts of ethylene glycol were blended and uniformly mixed under a nitrogen stream.
Next, 3-isocyanatomethyl-3,
5,5'-trimethylcyclohexyl isocyanate 2
22 parts, 1,6-hexamethylene diisocyanate 16
8 parts were added and heated at 110 ° C. for 3 hours. Then DM
F4142 parts, MEK2762 parts, diethanolamine 42 parts, 3-aminomethyl-3,5,5'-trimethylcyclohexylamine 102 parts were added and heated. Then, when the viscosity of 25,000 cps / 30 ° C. was reached at a concentration of 30%, the isocyanate residue in the solution was blocked with monoethanolamine to obtain a hydrophilic polyurethane resin solution having active hydrogen at the terminals and side chains.

After 30 parts of MEK and 2 parts of a polyfunctional polyisocyanate (Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) were uniformly mixed with 100 parts of the hydrophilic polyurethane resin solution, the mixture was used as in Example 1 using the mixed solution. To obtain a dry film.

The dry films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were obtained by heating them at 80 ° C. for 10 minutes and at 120 ° C.
After drying x10, aging was performed at 60C for 96 hours to obtain a cured film. Then, these cured films were peeled off from the release paper, and the water swelling ratio and the light resistance were measured by the methods described above. The results are shown in Table 1.

The light resistance was determined by irradiating the sample film in a fade meter (black panel temperature: 83 ° C.) for 100 hours and then measuring the degree of discoloration according to JIS L084.
The light discoloration resistance evaluated in five steps using the gray scale for discoloration of No. 4 and the light deterioration resistance judged by visual and tactile sensation of the film after irradiation for 100 hours were evaluated. The light degradation resistance was 5: no abnormality, 4: slightly cracked and sticky, 3: partially cracked and sticky, 2:
Cracked, sticky, 1: Cracked, sticky on the entire surface.

[0039]

[Table 1]

From Table 1, all of the crosslinked cured films obtained in Examples 1 to 3 of the present invention showed good results in water swelling and light fastness such as light discoloration resistance and light deterioration resistance. On the other hand, the film according to Comparative Example 1 was a non-crosslinked type and had good water swellability, but the light resistance of the film after irradiation with the fade meter for 100 hours was large. Comparative Example 2 was a film in which only the ends were crosslinked with polyisocyanate. The crosslink density was small, and light resistance deterioration was observed over the entire surface. Although the cured film of Comparative Example 3 was crosslinked with polyisocyanate at the terminals and side chains, the film itself was soft with a long main chain structure, so that the water swellability was too large and the light resistance deterioration was not good.

Example 4 A polyisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., manufactured by Nippon Polyurethane Industry Co., Ltd.) obtained by blocking 30 parts of MEK with 100 parts of the hydrophilic polyurethane resin solution having active hydrogen at the terminal and the side chain obtained in Example 1 and 30 parts of MEK -250
7) A mixed solution obtained by adding 5 parts and uniformly mixing was coated on release paper so that the dry film thickness became 10 μm, and heated at 100 ° C. for 2 minutes to prepare a dry film. Next, a polyurethane resin (Seiko Kasei Co., Ltd.,
Rackskin UD-108) 100 parts and polyisocyanate (Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) 8
And a solution prepared by mixing 20 parts of toluene with a 32 mesh gravure printer, dried at 100 ° C. for 1 minute, and laminated with a nylon plain fabric. Then 1
After heating at 50 ° C. for 2 minutes, and further aging at 60 ° C. for 48 hours, the release paper was peeled off to obtain a moisture-permeable waterproof fabric for dry clothing.

JIS L of the waterproof fabric thus obtained
The moisture permeability measured by the 1099A-1 method is 7200 g
/ M ² · 24 hrs, and a water resistance based on the hydrostatic method of JIS L 1092B method was 1.47 kgf / cm ^2, which was a good value.

[0043]

As described above, the present invention provides a resin composition comprising a hydrophilic polyurethane resin having an active hydrogen as a functional group at a terminal and a side chain and a crosslinking agent. The crosslinked cured film using
Since it is water-swellable, has excellent moisture permeability, and has good light resistance, it is extremely suitable for use in clothing and sanitary materials.

Claims (3)

[Claims] An active hydrogen is added to a terminal and a side chain obtained by reacting an organic diisocyanate with a monomer having two active hydrogens in a molecule and a polyfunctional monomer having three or more active hydrogens in a molecule. A resin composition having excellent water swellability, light resistance, and moisture permeability, comprising a hydrophilic polyurethane resin having a functional group as a functional group and a polyisocyanate or aminoplast crosslinking agent. 2. A hydrophilic polyurethane resin having an active hydrogen as a functional group at a terminal and a side chain, wherein a polyfunctional monomer having three or more active hydrogens in a molecule for providing the side chain with active hydrogen. Is used in an amount of 5 to 70 mol% of a monomer having two active hydrogens in the molecule. 3. The resin composition according to claim 1, wherein the water swelling ratio of the crosslinked film made of the resin composition is 50 to 300%.