JP3109528B2 - Waterproof cloth - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof cloth coated with a polyurethane resin solution containing a novel polyurethane resin as a main component.

[0002]

2. Description of the Related Art Conventionally, polyurethane resins have been used for coating agents, molding materials, synthetic leathers, surface treatment agents, paints, films, etc. because of their excellent mechanical strength and elasticity, and also applied to cloths. It is used as a waterproof cloth.

[0003] However, a waterproof cloth coated with a usual polyurethane resin has a drawback that it becomes stuffy when worn due to poor moisture permeability. In order to solve this problem, a method has been proposed in which a polyurethane resin solution is wet-solidified to make it microporous, but such a method requires complicated processing steps.

[0004] Further, it has been proposed to mix and apply a hygroscopic powder such as wood flour to a polyurethane resin solution, but there are drawbacks such as insufficient moisture permeability and rough texture. .

Further, a method has been proposed in which a polyoxyethylene glycol having a hygroscopic property is copolymerized in the main chain of the polyurethane resin. However, such a polyurethane resin has a problem that its water absorption is large and its durability is inferior.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a waterproof cloth coated with a polyurethane resin composition having excellent durability such as moisture permeability, water resistance and solvent resistance. Is what you do.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to develop a waterproof cloth coated with a novel polyurethane resin composition having the above excellent properties, and as a result, completed the present invention.

That is, the present invention radically polymerizes polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group. Or a macromonomer (A) obtained by copolymerizing the polyoxyethylene monoalkyl ether methacrylate and / or the polyoxyethylene monoalkyl ether acrylate with another monomer having a radical polymerizable unsaturated bond.
And a resin solution containing, as a main component, a polyurethane resin obtained by reacting at least one polyol (B) selected from the group consisting of polyester polyol, polyether polyol and polyester ether polyol with an organic polyisocyanate (C) as essential components Waterproof cloth, preferably 2 to 200 oxyethylene units in the polyoxyethylene chain of polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate. Preferably, the polyurethane resin contains 10 to 80% by weight of polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate based on the polyurethane resin. It is to provide a cloth.

Here, the macromonomer of the present invention refers to an oligomer having two or more hydroxyl groups at one end. Further, the polyurethane resin may have a urea bond in addition to the urethane bond.

The mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group used in the production of the macromonomer (A) of the present invention includes, for example, 1-
Mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-
Propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-
Propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3
-Propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

The polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate used in the production of the macromonomer (A) of the present invention has a polyoxyethylene chain length of preferably 2 as oxyethylene units. Or 200
, More preferably 4 to 100. Shorter polyoxyethylene chains tend to reduce moisture permeability, while longer polyoxyethylene chains tend to decrease mechanical strength. The alkoxy group is generally an oxyalkyl group having 1 to 4 carbon atoms.

Further, the polyoxyethylene monoalkyl ether methacrylate and / or the polyoxyethylene monoalkyl ether acrylate may contain an oxypropylene bond, an oxybutylene bond, an oxystyrene bond and the like.

The macromonomer (A) of the present invention comprises polyoxyethylene monoalkyl ether methacrylate and / or
Alternatively, it may be obtained by copolymerizing a monomer having a radical polymerizable unsaturated bond other than polyoxyethylene monoalkyl ether acrylate with polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate. .

Examples of the monomer having a radical polymerizable unsaturated bond other than polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl Examples include alkyl acrylates and / or methacrylates such as methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate, acrylonitrile, methacrylonitrile, styrene, and vinyl acetate. Further, glycidyl methacrylate, N, N-dimethylaminoethyl methacrylate or a salt thereof, methacryloyloxyethyl acid phosphate or a salt thereof, styrenesulfonic acid or a salt thereof, perfluorooctylethyl methacrylate, dimethylpolysiloxylpropyl methacrylate, and the like can be given. .

Although the macromonomer of the present invention can be produced by any known polymerization method, a solution polymerization method is preferred because it is used as a raw material for a polyurethane resin. Solvents for solution polymerization include, for example, aromatic hydrocarbons such as toluene and xylene, esters such as methyl formate, ethyl formate, methyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone methyl isobutyl ketone; methanol and ethanol. Alcohols such as propanol and butanol, ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ether esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate.

Examples of the polymerization catalyst for the solution polymerization include lauroyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexyl peroxide, diisopropylperoxydicarbonate, and di-2.
Organic peroxides such as -ethylhexylperoxycarbonate, di-2-ethoxyethylperoxydicarbonate, t-butylperoxybivalate and t-butylperoxyneodecanoate; and 2,2'-azobisisobutyi. Examples include azo compounds such as lonitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, and 4,4′-azobis-4-cyanovaleric acid.

The mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group, an organic solvent, a polymerization initiator, polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate, polyoxy Monomers having a radical polymerizable unsaturated bond other than ethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate may be added to the polymerization system at once, or added separately during polymerization. May be. The polymerization is usually carried out at a temperature of 35 to 150 ° C. with stirring.

The molecular weight of the macromonomer of the present invention is not particularly limited, but is preferably from 500 to 20,000. Examples of the polyester polyol used for the polyol (B) of the present invention include ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3- Methyl-
1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol,
Dipropylene glycol, tripropylene glycol,
Cyclohexane-1,4-diol, cyclohexane-
1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol,
One or more polyhydric alcohols such as pentaerythritriol, sorbitol, methylglycoside, etc. and succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Condensates with one or more polybasic acids or acid anhydrides such as acids, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, hexahydroisophthalic acid, etc. And the like. Further, ring-opening polymers such as γ-butyrolactone and ε-caprolactone using the polyol as an initiator are also exemplified. Furthermore, a polycarbonate diol such as poly (hexamethylene carbonate) diol may be used.

Examples of the polyether polyol used in the polyol (B) of the present invention include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and at least one of the above-mentioned polyhydric alcohols and polyamines as initiators. Single or two or more ring-opening polymers such as tetrahydrofuran and the like can be mentioned.

Examples of the polyester ether polyol used in the polyol (B) of the present invention include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran and the like using one or more of the above-mentioned polyester polyols as initiators. Homogeneous or two or more ring-opening polymers are exemplified.

The molecular weight of the polyol (B) used in the present invention is not particularly limited, but is usually from 500 to 500.
0. When the polyol (B) used in the present invention contains a polyoxyethylene chain, the content of the polyoxyethylene chain in the polyol (B) is preferably 10% by weight or less.

As the organic polyisocyanate (C) used in the present invention, for example, tolylene diisocyanate,
Aromatic diisocyanates such as diphenylmethane diisocyanate, naphthalene diisocyanate and phenylene diisocyanate, hexamethylene diisocyanate,
Aliphatic or alicyclic diisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene isocyanate, triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanate, and carbodiimide group. And polyisocyanates having an allophanate group and polyisocyanates having an isocyanurate group.

In the polyurethane composition of the present invention, a low molecular compound having two or more groups which react with an isocyanate group can be used in addition to the polyester polyol, polyether polyol and polyester polyether polyol.

Examples of the low molecular compound having two or more groups that react with an isocyanate group include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol,
Butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol,
Dipropylene glycol, tripropylene glycol,
Cyclohexane-1,4-diol, cyclohexane-
1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol,
Polyols such as pentaerythritol, sorbitol, methyl glycoside, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, hydrazine, piperazine, N,
N′-diaminopiperazine, 2-methylpiperazine,
Examples thereof include one or a mixture of two or more polyamines such as 4,4 'diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, diphenylmethanediamine, and methylenebisdichloroaniline.

The polyurethane resin of the present invention contains polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate in an amount of preferably 10 to 80% by weight, more preferably 2% by weight.
It contains 0 to 60% by weight. When the content of the polyoxyethylene chain is small, the moisture permeability tends to decrease, and when it is large, the mechanical strength tends to decrease.

The molecular weight of the polyurethane composition of the present invention is not particularly limited. When the polyurethane composition of the present invention has a low molecular weight, it can be used after crosslinking with a curing agent such as polyisocyanate. Alternatively, when the molecular weight is high, it can be used without crosslinking.

The polyurethane resin of the present invention is produced by reacting a macromonomer (A), a polyol (B) and an organic polyisocyanate (C) as essential components. The reaction order is not particularly limited. For example, a mixture of a macromonomer (A), a polyol (B), and a low molecular compound (D) having two or more groups reactive with an isocyanate group may be added to an organic polyisocyanate (C). , A prepolymer obtained by adding and reacting an organic polyisocyanate (C) to a mixture of a macromonomer (A) and a polyol (B) has two or more groups that react with isocyanate groups. Even when the low molecular compound (D) is added and reacted, the prepolymer obtained by adding and reacting the organic polyisocyanate (C) to the macromonomer (A) has two groups that react with the polyol (B) and the isocyanate group.
You may react by adding the low molecular compound (D) which has more than one. A monomer (A) having a reactive double bond, a polyol (B), a low-molecular compound having two or more groups that react with an isocyanate group, and / or an organic polyisocyanate (C) may be divided and added. .

Macromonomer (A), polyol (B)
The ratio of the low-molecular compound having two or more groups that react with the isocyanate group to the organic polyisocyanate (C) is not particularly limited, but the ratio of the total of the groups that react with the isocyanate group to the isocyanate group is usually 2: 1 ~
It is carried out at a ratio of 1: 2, preferably 1.2: 1 to 1: 1.2.

The reaction comprising the macromonomer (A), the polyol (B) and the organic polyisocyanate (C) as essential components can be carried out in the absence of a solvent, in an organic solvent or in water. 20-150 ° C,
Preferably, it is carried out at 30 to 100 ° C.

Examples of the organic solvent include esters such as methyl acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide; Amides such as acetamide, alcohols such as methanol, ethanol, propanol and butanol, ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ether esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate Or a mixture of two or more. These organic solvents can be added at the beginning, during, at the end or at any stage of the reaction.

In the production of the polyurethane resin of the present invention, a tertiary amine catalyst and / or an organometallic catalyst may be used at the beginning and / or during the reaction, if necessary, to accelerate the reaction.

If necessary, an alcohol such as methanol, ethanol and propanol and / or an amine compound such as dimethylamine, diethylamine, dipropylamine and dibutylamine may be added to the reaction at the beginning, during and / or after the reaction.
Alternatively, or finally, the molecular weight of the resulting polyurethane resin can be adjusted.

A polyurethane resin composition can be obtained by adding an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a dye, a pigment, a filler and the like to the polyurethane resin obtained in the present invention, if necessary. it can.

The waterproof cloth of the present invention can be obtained by applying the obtained polyurethane resin composition to cloth. As a method of applying, for example, in addition to a method of directly applying to a cloth with a doctor knife coater, a roll coater, etc., a film of a polyurethane resin composition is formed on a support having a releasing property, and the film is adhered to the cloth. It is also obtained by doing.

The cloth used in the present invention includes, for example, a woven cloth of natural or synthetic fibers such as cellulose, polyester and nylon.

[0036]

The following examples are given, but the present invention is not limited to these examples. In the text, “parts” are based on weight.

The method for preparing the polyurethane resin film and the method for testing moisture permeability, water resistance and solvent resistance are as follows. <Production method of polyurethane resin film> A polyurethane resin solution was cast on release paper and dried at 80 ° C for 30 minutes.
Heat treatment at 20 ° C for 5 minutes, and further about 20 ° C, relative humidity about 6
It was left in an atmosphere of 0% for 3 days to form a film of about 30 microns.

<Moisture Permeability Test> The film produced by the above method was measured according to JIS Z-0208. <Water resistance (water swelling degree) test> The film prepared by the above method was immersed in water at about 25 ° C for 1 hour, and the area increase rate α (%) of the film in a wet state was determined by the following equation.

Α = (A−A ₀ ) × 100 ÷ A ₀ where A is the surface area after immersion in water, and A ₀ is the surface area before immersion in water. <Solvent resistance (perchrene swelling degree) test> The film prepared by the above method was immersed in perchlorethylene at about 25 ° C. for 1 hour, and the area increase rate β (%) of the film in a wet state was determined by the following formula. I asked.

Β = (A′−A ₀ ) × 100 ÷ A ₀ where A ′ is the surface area after immersion in perchlorethylene,
₀ is the surface area before immersion in perchlorethylene.

Example 1 Macromonomer obtained by radical polymerization of polyoxyethylene monomethyl ether methacrylate having a molecular weight of 2000 (macromonomer having a diol group at one end obtained by polymerizing polyoxyethylene monomethyl ether methacrylate having a molecular weight of 500 in the presence of thioglycerin) ) 200
Parts, polybutylene adipate diol having a molecular weight of 2000, 200 parts, butylene glycol 36 parts, diphenylmethane diisocyanate 154 parts, dimethylformamide 1
367 parts were mixed and reacted at 80 ° C. to obtain a polyurethane solution having a resin concentration of 30% and a viscosity of 520 poise. This film had a moisture permeability of 3900 mg / m ² · 24 hr, and the water swelling degree and the perclene swelling degree were 7.2% and 26.1%, respectively.

Example 2 200 parts of polybutylene adipate diol having a molecular weight of 2,000 and 234 parts of toluene were mixed with 200 parts of the macromonomer having a diol group at one end used in Example 1, and 104 parts of dicyclohexylmethane diisocyanate and 104 parts of octylic acid Add 0.03 parts of tin and 100 ℃
404 parts of toluene and 6 parts of isopropanol
In addition to a mixed solution of 38 parts and 43 parts of isophoronediamine, a polyurethane solution having a resin concentration of 30% and a viscosity of 350 poise was obtained. This film has a moisture permeability of 4200 mg / m ² · 24
In hr, the water swelling degree and the perchrene swelling degree are each 5.
4% and 34%.

Example 3 218 parts of the macromonomer having a diol group at one end used in Example 1, 218 parts of polybutylene adipate diol having a molecular weight of 2,000, 9 parts of butylene glycol, and tolylene diisocyanate (2,4- and 2,2) The isomer ratio of 6-80 is 20) 54 parts, 250 parts of methyl ethyl ketone and 250 parts of toluene are mixed, and 0.03 part of stannous octoate is added and reacted at 80 ° C. to give a resin concentration of 50%.
A polyurethane solution having a viscosity of 760 poise was obtained. To 100 parts of this polyurethane solution, 8 parts of Chrisbon NX (a polyisocyanate-based crosslinking agent manufactured by Dainippon Ink and Chemicals, Inc., isocyanate group content: about 13%) and Chrisbon
A film was prepared by mixing 3 parts of Axel HM.

This film has a moisture permeability of 5060 mg / m ² · 24 hr.
The degree of water swelling and the degree of perchulene swelling are 3.8
% And 36.1%. Example 4 To 100 parts of the polyurethane resin solution obtained in Example 1, 40 parts of dimethylformamide and 20 parts of Dilac L color (a coloring agent manufactured by Dainippon Ink and Chemicals, Inc.) were added.
The coating was made uniform, coated on a release paper so that the solid content film thickness became 0.01 mm, and dried at 90 ° C. for 3 minutes. A mixture of Chrisbon NX 8 parts, Chrisbon Accel HM 3 parts, methyl ethyl ketone 30 parts and dimethylformamide 10 parts was applied to 100 parts of the polyurethane resin solution obtained in Example 3 so that the solid content film thickness was 0.02 mm. After drying at 120 ° C. for 1 minute, a knitted nylon tricot fabric was immediately pressed and heat-treated at 120 ° C. for 3 minutes. Next, the release paper was peeled off and treated with a silicone-based water repellent to obtain a waterproof cloth. This waterproof cloth has a soft texture, a water pressure of 2,000 mm or more, a water column of 100 points, and a moisture permeability of 42.
00 mg / m ² · 24 hr. JIS L
Even if the water washing according to the -1042 F-1 method was repeated five times, there was no appearance damage. Also, JIS L-08
Even if dry cleaning according to 74 is repeated 5 times,
There was no appearance damage.

[0045]

The polyurethane resin of the present invention and the polyurethane resin composition containing this resin as a main component are excellent in moisture permeability, water resistance and solvent resistance, and the waterproof cloth coated with this is excellent in moisture permeability and durability. It is useful as a waterproof cloth.

──────────────────────────────────────────────────の Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/62 C09D 175/04-175/16

Claims (3)

(57) [Claims] A polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether methacrylate in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group.
Alternatively, polyoxyethylene monoalkyl ether acrylate is subjected to radical polymerization, or the polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate is copolymerized with another monomer having a radical polymerizable unsaturated bond. a macromonomer obtained by polymerizing (a), obtained by reacting a polyester polyol, at least one polyol selected from the group consisting of polyether polyols and polyester ether polyol (B) and an organic polyisocyanate (C) as essential components It is obtained by applying a resin solution containing polyurethane resin as a main component.
And waterproof cloth. 2. The waterproof fabric according to claim 1, wherein the polyoxyethylene chain of the polyoxyethylene monoalkyl ether methacrylate and / or the polyoxyethylene monoalkyl ether acrylate has 2 to 200 oxyethylene units. . 3. The waterproof according to claim 1, wherein the polyurethane resin contains 10 to 80% by weight of polyoxyethylene monoalkyl ether methacrylate and / or polyoxyethylene monoalkyl ether acrylate. cloth.