JP2009203592A - Coating material for fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material for coating surfaces of fabrics to obtain fabrics excellent in water proofness and tear strength for clothing and tent uses. <P>SOLUTION: The coating material for fabrics composed of polyester fibers or nylon fibers comprises a polyurethane resin solution prepared by copolymerizing a polysiloxane (A) one end of which is a functional group non-reactive with isocyanate groups and the other end of which has two primary hydroxy groups, an organic diisocyanate (B) and further a polyol (C) having hydroxy groups on its both ends. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides a fabric for garments and tents with improved waterproofness and excellent tear strength by coating a copolymer polyurethane resin solution on a fabric made of polyester fiber or nylon fiber. The present invention relates to a coating material that can be applied.

  Conventionally, woven fabrics of polyester fibers or nylon fibers (hereinafter referred to as woven fabrics) are often used as clothing and tent fabric materials. For these woven fabrics, for the purpose of further improving waterproofness, windproof property, moisture permeability and the like, many techniques for coating a solution of acrylic resin and urethane resin on the woven fabric have been proposed and implemented.

  However, although these properties can be improved by applying these synthetic resin liquids to the woven fabric, there is a problem that the tear strength is extremely reduced. For this reason, it is proposed to coat the woven fabric with a polysiloxane-modified polyurethane resin having hydroxyl groups at both ends after pretreatment with various water repellent materials such as perfluorocarbon, ethylene-urea and triazine. (Patent Document 1) has been implemented, but the level is still insufficient.

Further, in the present invention, an organopolysiloxane (A) represented by the following general formula (1) is used as one of the main components in obtaining a coating material. A method for producing a silicone-modified polyurethane using such an organopolysiloxane (A) as one of the main components and a method for producing a polyurethane resin for synthetic leather have also been proposed (Patent Documents 2 and 3). Silicone-modified polyurethane has water repellency, oil repellency, low friction, and antithrombotic properties. Patent Document 3 is a polyurethane resin for synthetic leather that has a low wear coefficient and excellent wear resistance. Thus, the present invention for obtaining a coating material for providing a fabric for clothing and tent having an excellent tear strength is different from the object of the invention.
Japanese Patent Laid-Open No. 1-61243 JP-A 63-289012 JP-A-3-167212

  As a result of intensive studies aimed at improving the waterproofness and tear strength of clothing and tent fabrics, the present invention has revealed that the organopolysiloxane (A) represented by the general formula (1) and the organic diisocyanate (B) A polyurethane resin that has been reacted as an essential component and has an organopolysiloxyl group in the molecular side chain is a conventional organopolysiloxane (D) represented by the following general formula (2) having primary hydroxyl groups at both ends. As a result, the present inventors have found that the tear strength is dramatically improved as compared with the silicone copolymer polyurethane resin thus obtained.

  The invention described in claim 1 includes an organopolysiloxane (A) having one end which is a non-reactive functional group with an isocyanate group and two primary hydroxyl groups at the other end, and an organic diisocyanate (B). Further, the present invention is characterized by a polyester fiber or nylon fiber fabric coating material comprising a polyurethane resin liquid obtained by copolymerizing a polyol (C) having hydroxyl groups at both ends.

  The invention according to claim 2 is characterized in that, in the invention according to claim 1, the organopolysiloxane (A) is copolymerized in a polyurethane resin solution by 2% or more.

According to the coating material of the present invention described in the above-mentioned claims, a coating film excellent in waterproofness, tearing strength and the like can be formed by coating the surface of a fabric used for clothing or tent.

    Hereinafter, the present invention will be described in detail. The present invention relates to a polyurethane comprising a compound having at least two isocyanate groups and a compound having at least two hydroxyl groups, and in the reaction for forming a urethane bond, as a part of the hydroxyl group-containing compound, A silicone-modified polyurethane resin solution characterized by copolymerizing 2% or more of the polysiloxane (A) silicone compound in the entire polyurethane resin, and can be directly coated on a woven fabric of polyester or nylon by a knife coater. By dip coating, the tear strength of the woven fabric having waterproofness and windproof property was successfully improved.

  The constituent component of the silicone-modified polyurethane resin used in the present invention is not particularly limited. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl. Polyether glycols such as polyethylene polyols, polyethylene glycols, polytetramethylene glycols, and the like, and polycarbonate polyols having an average molecular weight of 500 to 5000, consisting of alkylene glycols such as glycols and dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and phthalic acid Poly epsilon-caprolactone polyol is used. In addition, the organopolysiloxane (A) represented by the general formula (1), which is an essential component of the present invention, is used in combination.

Organic diisocyanates include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI). ), Isophorone diisocyanate (IPDI) or the like.

  Next, as chain extenders, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycols such as neopentyl glycol, ethylenediamine, hexamethylenediamine, isophoronediamine (IPDA), Diamines such as anhydrous piperazine can be used.

  As the polymerization solvent, various organic solvents such as methyl ethyl ketone (MEK), dimethylformamide (DMF), toluene, xylene, cyclohexanone, and tetrahydrofuran can be used.

When producing the polyurethane resin as the coating material of the present invention, a catalyst and a stabilizer can be used if necessary. Examples of the catalyst include nitrogen-containing compounds such as triethylamine and triethylenediamine, and organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate.

  As the stabilizer, stabilizers against ultraviolet rays such as substituted benzotriazoles, and stabilizers against heat such as phenol derivatives can be used.

  The polyurethane resin in the present invention is usually obtained by a solution reaction, the non-volatile content is 20 to 50% by weight, the solution viscosity is 1000 to 100,000 mPa · s / 25 ° C. Adjust the viscosity. Moreover, in order to improve adhesiveness with a woven fabric and durability, a crosslinking agent can also be mix | blended. As the crosslinking agent, aminoplast resins such as melamine-formaldehyde resin, polyfunctional polyisocyanate, and the like are suitable.

  The woven fabric of polyester fiber and nylon fiber used in the present invention has been conventionally used for clothing, tents, etc., and is not particularly limited, but those that have been dyed and water-repellent processed are used. That's fine.

EXAMPLES Hereinafter, although this invention is demonstrated in detail by a synthesis example and an Example, this invention is not limited at all by these synthesis examples and Examples. All the parts are parts by weight.
(Synthesis Example 1)

140 parts of 1,4-butanediol adipate having an average molecular weight of 2000, 9.4 parts of 1,6-hexanediol, 86.5 parts of DMF and 8 mg of dioctyltin dilaurate were charged into a flask equipped with a stirrer, and nitrogen gas was sealed therein at 50 ° C. Warmed to. Thereafter, 52.4 parts of H ₁₂ MDI was added, and the prepolymer reaction was performed by heating at 90 to 100 ° C. for about 90 minutes.

Thereafter, 159 parts of DMF and 246 parts of MEK were added while cooling to adjust the liquid temperature to 40 ° C. Further, 8.5 parts of IPDA were gradually added dropwise to carry out a thickening reaction. When the viscosity reached 20000 mPa · s / 25 ° C., the reaction was stopped by adding monoethanolamine to the remaining NCO to obtain a solid content. A 30% polyurethane elastomer resin solution was obtained. A 30-40 μm thick film produced using this resin solution had a 100% modulus of 5 MPa.
(Synthesis Example 2)

The amount used of 1,4-butanediol adipate having an average molecular weight of 2000 during the blending in Synthesis Example 1 was reduced to 126 parts, and 14 parts of organopolysiloxane (D) having an average molecular weight of 2000 (silicone amount 7). %) A polyurethane elastomer resin solution having a solid content of 30% and a viscosity of 23000 mPa · s / 25 ° C. was obtained except that the compound was used. A 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 4.8 MPa.
(Synthesis Example 3)

1,4-butanediol adipate having an average molecular weight of 2000, 128.5 parts of organopolysiloxane (A) having an average molecular weight of 5000, 14.4 parts (silicone amount 7%), 9.1 parts of 1,6-hexanediol, DMF86 .5 parts and dioctyltin dilaurate 8 mg were charged into a flask equipped with a stirrer, and nitrogen gas was sealed and heated to 50 ° C. Thereafter, 50.2 parts of H ₁₂ MDI was added, and the prepolymer reaction was performed by heating at 90 to 100 ° C. for about 90 minutes.

Thereafter, 159 parts of DMF and 246 parts of MEK were added while cooling to adjust the liquid temperature to 40 ° C. Furthermore, 8.1 parts of IPDA were gradually added dropwise to carry out a thickening reaction. When the viscosity reached 30000 mPa · s / 25 ° C., the reaction was stopped by adding monoethanolamine to the remaining NCO to obtain a solid content. A 30% polyurethane elastomer resin solution was obtained. A 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 4.8 MPa.
(Synthesis Example 4)

The same composition and operation as in Synthesis Example 3 except that 1,4-butanediol adipate having an average molecular weight of 2000 in the blending in Synthesis Example 3 described above was changed to poly 1,6-hexane carbonate diol having an average molecular weight of 2000. Reaction was performed to obtain a polyurethane elastomer resin solution having a solid content of 30% and a viscosity of 22000 mPa · s / 25 ° C. A 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 6 MPa.
(Synthesis Example 5)

140 parts of 1,4-butanediol adipate having an average molecular weight of 2000 in the blending in Synthesis Example 1 was reduced to 138 parts, and 2.0 parts of organopolysiloxane (A) having an average molecular weight of 5000 (silicone) The reaction was carried out in the same composition and operation as in Synthesis Example 1 except that the amount was 1%), and a polyurethane elastomer resin solution having a solid content of 30% and a viscosity of 20000 mPa · s / 25 ° C. was obtained. The 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 4.5 MPa.
(Synthesis Example 6)

12.6 parts of 1,4-butanediol adipate having an average molecular weight of 2000, 14.8 parts of organopolysiloxane (A) having an average molecular weight of 5000 (silicone amount 7%), 10.7 parts of 1,4-butanediol, DMF86 .5 parts and dioctyltin dilaurate 8 mg were charged into a flask equipped with a stirrer, and nitrogen gas was sealed and heated to 50 ° C. Thereafter, 62.1 parts of H ₁₂ MDI was added, and the prepolymer reaction was performed by heating at 90 to 100 ° C. for about 90 minutes.

Thereafter, 159 parts of DMF and 246 parts of MEK were added while cooling to adjust the liquid temperature to 40 ° C. Further, 10.1 parts of IPDA was gradually added dropwise to carry out a thickening reaction. When the viscosity reached 21000 mPa · s / 25 ° C., the reaction was stopped by adding monoethanolamine to the remaining NCO, A 30% polyurethane elastomer resin solution was obtained. A 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 12 MPa.
(Synthesis Example 7)

19.7 parts of 1,4-butanediol adipate with an average molecular weight of 1000, 11 parts of organopolysiloxane (D) with an average molecular weight of 2000 (silicone amount 5%), 47.8 parts of polyethylene glycol with an average molecular weight of 1000, 1,4 -13.5 parts of butanediol, 90.1 parts of DMF and 8 mg of dioctyltin dilaurate were charged into a flask equipped with a stirrer, and nitrogen gas was sealed and heated to 50 ° C. Thereafter, 68.3 parts of MDI was added and reacted at 70 to 80 ° C., and 155.4 parts of DMF and 246 parts of MEK were added along with the thickening of the solution, and when the viscosity reached 25000 mPa · s / 25 ° C. The reaction was stopped by adding monoethanolamine to NCO to obtain a polyurethane elastomer resin solution having a solid content of 30%. The 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 4.5 MPa.
(Synthesis Example 8)

  72.2 parts of 1,4-butanediol adipate with an average molecular weight of 1000, 10.1 parts of organopolysiloxane (A) with an average molecular weight of 5000 (silicone amount 5%), 47.2 parts of polyethylene glycol with an average molecular weight of 1000, 1 , 4-butanediol 13.4 parts, DMF 90.1 parts and dioctyltin dilaurate 8 mg were charged into a flask equipped with a stirrer, nitrogen gas was sealed, and the mixture was heated to 50 ° C. Thereafter, 67.4 parts of MDI was added and the reaction was carried out at 70 to 80 ° C., and 155.4 parts of DMF and 246 parts of MEK were added along with the thickening of the solution, and when the viscosity reached 35000 mPa · s / 25 ° C. The reaction was stopped by adding monoethanolamine to NCO to obtain a polyurethane elastomer resin solution having a solid content of 30%. A 30 to 40 μm thick film produced using this resin solution had a 100% modulus of 4.2 MPa.

100 parts of the polyurethane elastomer resin solution obtained in Synthesis Example 3 above was diluted with 40 parts of DMF and 40 parts of MEK, and 3.5 parts of Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd., 75% isocyanate curing agent) was added uniformly. By mixing, a coating solution having a viscosity of 300 mPa · s / 25 ° C. was prepared. The obtained coating solution is applied to (1) nylon woven fabric for clothing, (2) 10 g / m ² · dry by dipping, and dried for 2 minutes in a drying oven at 120 ° C. for clothing. A processed fabric for a tent was obtained.

  Using the polyurethane elastomer resin solution obtained in Synthesis Example 4 above, treatment was performed in the same manner as in Example 1 to obtain processed fabrics for clothing and tents.

100 parts of the polyurethane elastomer resin solution obtained in Synthesis Example 8 above was diluted with 30 parts of MEK to prepare a coating solution having a viscosity of 5000 mPa · s / 25 ° C. The resulting coating liquid (1) to the clothing of nylon fabric, 30 g / m 2 · ^dry was applied by direct coating process, to obtain a finished fabric for clothing and dried for 2 minutes in a drying oven at 120 ° C..

100 parts of the polyurethane elastomer resin solution obtained in Synthesis Example 3 above was diluted with 30 parts of MEK, and 3.5 parts of Coronate HL was added and mixed uniformly to prepare a coating solution having a viscosity of 4000 mPa · s / 25 ° C. The obtained coating solution is applied to (1) nylon woven fabric for clothing, (2) 30 g / m ² · dry by direct coating, and dried for 2 minutes in a drying oven at 120 ° C. for clothing. A processed fabric for a tent was obtained.

The polyurethane elastomer resin solution obtained in Synthesis Example 6 was used and treated in the same manner as in Example 1 to obtain processed fabrics for clothing and tents.
(Reference Example 1)

Using the polyurethane elastomer resin solution obtained in Synthesis Example 1 above, a processed fabric for clothing and tent was obtained by the same method as in Example 1 above.
(Reference Example 2)

Using the polyurethane elastomer resin solution obtained in Synthesis Example 2, a processed fabric for clothing and tent was obtained by the same method as in Example 1 above.
(Reference Example 3)

Using the polyurethane elastomer resin solution obtained in Synthesis Example 5 above, a processed fabric for clothing and tent was obtained by the same method as in Example 1 above.
(Reference Example 4)

  Using the polyurethane elastomer resin solution obtained in Synthesis Example 7 above, a processed fabric for clothing and tent was obtained by the same method as in Example 1 above.

  In the above, the fabric made of nylon fibers used for clothing uses 6-nylon twill fabric (both warp and weft 75d / 36f, warp density 133 / inch, weft density 90 / inch), and fluorine water repellent A 5% aqueous solution of the agent Asahi Guard AG710 was padded, dried and cured. The fabric made of polyester fibers used for tents uses polyester twill fabrics (both warp and weft 100d / 50f, warp density 171 / inch, weft density 84 / inch), and fluorine-based water repellent Asahi. A 5% aqueous solution of Guard AG710 is padded, dried and cured.

  The coating fabrics obtained in Examples 1 to 4 and Reference Examples 1 to 6 were subjected to performance tests such as tear strength, A-1 moisture permeability, and water pressure resistance. The results are shown in Table 1. The evaluation methods and evaluation criteria for these tests are as follows.

  Tear strength test: Measured by A-1 method (single tank method) of JIS-L 1096.

  Moisture permeability test: Measured by JIS-L 1099 calcium chloride method (A-1 method).

  Water pressure resistance test: Measured by JIS-L 1092 B method (high water pressure method).

  From Table 1 above, Examples 1, 2 and 5 of the present invention used the resin solutions obtained in Synthesis Examples 3, 4 and 6 in which organopolysiloxane (A) was copolymerized within the scope of the present invention. As a result, the tear strength was dramatically improved over the woven fabric alone, and when used for clothing and tents, a product with excellent waterproofness and durability was obtained.

  In Example 3, the resin solution obtained in Synthesis Example 8 is used, and since polyester and polyethylene glycol are used in combination, when used for clothing, the moisture permeability is high and the tear strength is high. Product was obtained.

  Example 4 uses the resin solution obtained in Synthesis Example 3 in the same manner as in Example 1, lowers the dilution rate than in Example 1, and directly coats one side of the woven fabric with a coating solution having a high viscosity. A product with a soft texture and high tear strength was obtained.

  Reference Example 1 uses the resin solution obtained in Synthesis Example 1 without silicone copolymerization, and Reference Example 2 copolymerizes organopolysiloxane (D) that is outside the scope of the present invention. The product obtained by using the resin solution obtained in Synthesis Example 2 and the product obtained by forming a film on the surface using these resin solutions has a tear strength lower than that of the woven fabric alone and has a poor durability. Met.

  In Reference Example 3, the resin solution obtained in Synthesis Example 5 obtained by copolymerizing organopolysiloxane (A) was used. However, since the amount of silicone was small, it was torn from the products obtained in Examples 1 and 2 of the present invention. The strength was low.

  Reference Example 4 uses the resin solution obtained in Synthesis Example 7 obtained by copolymerizing organopolysiloxane (D), which is outside the scope of the present invention. The moisture permeability is similarly good as compared with Example 3. However, the tear strength was low and the product was insufficient.

Claims (2)

  Polyol having one end with a functional group that is non-reactive with an isocyanate group, an organopolysiloxane (A) having two primary hydroxyl groups at the other end, an organic diisocyanate (B), and a hydroxyl group at both ends (C), a polyester fiber or nylon fiber fabric coating material comprising a polyurethane resin liquid obtained by copolymerization with (C).   The coating material for a fabric according to claim 1, wherein the organopolysiloxane (A) is copolymerized in a polyurethane resin by 2% or more.