WO2016143136A1

WO2016143136A1 - Moisture permeable waterproof film and composite fabric layered therewith

Info

Publication number: WO2016143136A1
Application number: PCT/JP2015/057374
Authority: WO
Inventors: 榎本　雅穗; 表　雄一郎; 彩景尹; 鉉周崔; 宰源呉
Original assignee: 榎本　雅穗; 東洋紡Ｓｔｃ株式会社; 株式会社徳成
Priority date: 2015-03-12
Filing date: 2015-03-12
Publication date: 2016-09-15

Abstract

The present invention provides: a film having high dew-suppressive capabilities in a low-temperature state and excellent moisture-permeability in a high temperature state; and a moisture permeable waterproof fabric using this film, which is suitable for precipitation (snow) use, sports use, outdoor use, work use, and the like. This moisture permeable waterproof film is characterized by: containing a polyurethane resin modified with an acrylic resin; and having an LCST (lower critical solution temperature).

Description

Moisture permeable waterproof film and composite fabric laminated therewith

The present invention relates to a film containing a polyurethane resin modified with an acrylic resin having LCST (lower critical eutectic temperature), and in particular for various apparel applications such as for rain (snow), for sports, for outdoor use, for work, etc. The present invention relates to a moisture permeable waterproof film used in the above.

Moisture-permeable and waterproof fabrics that have the characteristics of passing moisture (breathable) but not passing water (waterproof) have moisture permeability, so the function of releasing water vapor from sweating to the outside of clothes and water resistance. Therefore, it has a function of preventing rain from entering the clothes, and such a moisture-permeable and waterproof fabric is widely used in sports clothing and cold clothing. Among them, it is widely used as a clothing material for sports, outdoor, and outdoor work with a high amount of sweat, and is now an indispensable clothing material especially in the skiing, snowboarding, athletic and mountaineering fields.

As a fabric having both moisture permeability and waterproof properties, for example, a high density woven fabric in which yarns are woven in high density, and a resin such as polyurethane resin, polyester resin, nylon resin, polytetrafluoroethylene resin are used. There are known coatings and films formed from these resins, which are bonded to a fabric through an adhesive. Among these, a polyurethane resin film having a particularly high hydrophilicity, a microporous polytetrafluoroethylene resin coated on the surface of the fabric, and a porous film formed by using a so-called wet coagulation method and using a polyurethane resin. Are formed on one side of the fabric, etc., which are evaluated in terms of both moisture permeability and waterproofness and are widely accepted in the market.

Specifically, for example, as a fabric using a polyurethane resin film having increased hydrophilicity, a film formed from a hydrophilic polyurethane resin obtained by copolymerizing a highly hydrophilic ether polyol component such as polyethylene glycol in the soft segment portion. Many bonded materials have been developed (for example, Patent Documents 1 and 2). However, such a moisture permeable waterproof film has insufficient performance due to swelling of the membrane surface when water is absorbed, resulting in poor wearing comfort, poor appearance, and poor washing durability. There were many. In addition, due to the effect of lowering the moisture permeability due to the swelling of the film surface, the moisture permeability of the fabric is not so high during exercise and there is a problem such as a feeling of stuffiness. On the other hand, when the amount of the hydrophilic component used is reduced and the swelling property of the film with respect to water is lowered, the moisture permeability during exercise is improved. However, at the time of rest immediately after exercise, condensation occurs in the clothes due to the saturated water vapor pressure accompanying the temperature drop in the clothes, but the film is not swellable to water, so the water absorption for the condensation is not in time, resulting in stuffiness in the clothes. There were also problems such as causing sweat chills.

In addition, a moisture-permeable waterproof fabric laminated with a microporous polyurethane film or polytetrafluoroethylene film (for example, Patent Documents 3 to 4) exhibits excellent effects in both moisture permeability and waterproof properties, but has a porous structure. The manufacturing equipment and process for forming the film are complicated, it is difficult to manufacture the film easily, and the product becomes very expensive.

Furthermore, as a moisture-permeable waterproof fabric that emphasizes dew condensation suppression performance, a wet coagulation method is adopted, and a porous film formed using a polyurethane resin is formed on one side of the fabric, for example, a polyurethane resin for wet processing There are proposed ones in which a hydrophilic polyurethane resin is mixed and processed into a fabric (Patent Document 5), and a fabric processed by adding a sulfonic acid soda compound to a polyamino acid polyurethane resin (Patent Document 6). However, although these fabrics are excellent in dew condensation suppression performance, they cannot be said to have good water resistance and washing durability when worn.

Further, as a moisture-permeable waterproof fabric that emphasizes dew condensation suppression performance and adopting a dry method, for example, an amino resin powder is proposed (Patent Document 7). However, the fabric of Patent Document 7 has insufficient washing durability and wear resistance, and performance as a clothing fabric is insufficient. On the other hand, a fabric in which a wet-processed cloth is overcoated with a hydrophilic polyurethane resin has also been proposed (Patent Document 8). However, since it takes time and effort to process, the manufacturing cost increases, and the wet-processed cloth is used. Also, the washing durability was insufficient.

By the way, a temperature-responsive polymer that exhibits different performance in response to temperature stimulation is known. As a material using such a temperature-responsive polymer, there is a moisture-permeable waterproof fabric using a polyurethane resin whose glass transition temperature is adjusted to a range of about −20 to 20 ° C. (Patent Documents 9 to 11). These moisture-permeable and waterproof fabrics have low moisture permeability according to JIS L 1099 B-1 method when the body temperature is low, such as at rest, and the same method when body temperature is high, such as immediately after active exercise. The moisture permeability to be measured is improved. This is a phenomenon that takes advantage of the fact that the transmittance of vaporized water (water vapor) increases with the glass transition temperature as a boundary. This makes it easier for water vapor generated in the body to escape to the outside in a high temperature state. However, these fabrics cannot sufficiently exhibit the dew condensation suppressing performance of absorbing liquefied moisture on the moisture permeable waterproof fabric in a low temperature state.

JP 11-49875 A JP 11-269773 A JP-A-4-41778 JP 58-166036 A JP-A-9-228253 Japanese Unexamined Patent Publication No. 63-145482 JP-A-8-209541 JP-A-11-61648 JP-A-6-49169 WO94 / 00631 Publication JP-A-5-272061

Under such circumstances, the present invention is a film having a high dew condensation suppressing performance in a low temperature state and excellent in moisture permeability at a high temperature state, and for rain (snow), sports use, outdoor use, work use and the like using the film. An object of the present invention is to provide a suitable moisture-permeable waterproof fabric.

As a result of intensive studies to solve the above problems, the present inventors have obtained a resin obtained by modifying an acrylic resin having LCST (Lower Critical Solution Temperature) as a temperature responsive polymer with a urethane resin. When used, the present invention was completed by finding that a film made of the resin as a raw material exhibits high water absorption at a low temperature and exhibits appropriate moisture permeability at a high temperature.

That is, the moisture-permeable waterproof film according to the present invention includes a polyurethane resin modified with an acrylic resin and has LCST. The moisture-permeable and waterproof film of the present invention is characterized in that the moisture-permeable and waterproof film has an LCST of 0 ° C. or more and 40 ° C. or less, and the moisture-permeable and waterproof film does not exhibit water solubility at or below the LCST. The acrylic resin is obtained by polymerization from a monomer mixture for an acrylic resin containing N-isopropylacrylamide and a hydroxyl group-containing (meth) acrylate as essential components. More preferably, it contains a monomer having an α, β-unsaturated ethylenic bond. Moreover, it is preferable that the polyol which comprises the said polyurethane resin contains polyether polyol. Furthermore, moisture-permeable waterproof film of the present invention, the water pressure is below 450kPa than 50 kPa, B-1 moisture permeability under 43 ° C. atmosphere or less 20000g / m ² · 24h or more 50000g / m ² · 24h, 13 B-1 moisture permeability under ℃ atmosphere or less 12000 g / m ² · 24h or more 16000g / m ² · 24h, the rate of change of water absorption before and after the LCST is 2 to 5.
The present invention also includes a composite fabric characterized by laminating the moisture-permeable and waterproof film on a base fabric.

According to the present invention, it is possible to obtain a moisture-permeable waterproof film that exhibits high water absorption at low temperatures and exhibits moderate moisture permeability at high temperatures.

FIG. 1 is a graph for LCST measurement in Examples 1-2 and Comparative Examples 1-3.

The moisture permeable waterproof film according to the present invention includes a polyurethane resin modified with an acrylic resin and has an LCST. In this invention, the resin which modified | denatured the acrylic resin which has LCST with the urethane resin is used as a raw material which comprises a moisture-permeable waterproof film. In this way, by reacting the acrylic resin and each component constituting the polyurethane resin, the polyurethane component serves as a water-insoluble component and adjusts the balance between the hydrophilicity and hydrophobicity of the moisture permeable waterproof film. Can do.

The moisture permeable waterproof film according to the present invention preferably has a moisture permeable waterproof film having an LCST of 0 ° C. or higher and 40 ° C. or lower, and the moisture permeable waterproof film has a property of not exhibiting water solubility even at LCST or lower. As a temperature-responsive polymer, poly N-isopropylacrylamide (PNIPAM) obtained by polymerizing N-isopropylacrylamide (NIPAM) is known, and the LCST of NIPAM homopolymer is usually about 32 ° C. NIPAM homopolymer exhibits hydrophilicity and becomes water-soluble at 32 ° C. or lower. However, if the film dissolves in water under a normal temperature condition of 32 ° C. or lower, the film is placed in a room temperature and wet environment. It is difficult to apply to various daily necessities used in, and it is difficult to fully utilize the temperature responsiveness of PNIPAM. The present invention provides a moisture permeable waterproof film adjusted to have an LCST of 0 ° C. or more and 40 ° C. or less, taking advantage of the temperature response characteristics of NIPAM. Therefore, in this invention, the kind and quantity of each component which comprise a moisture-permeable waterproof film are adjusted. The present invention is described in detail below.

<Acrylic resin>
The acrylic resin used in the present invention is obtained by radical polymerization from a monomer mixture for acrylic resin containing N-isopropylacrylamide and hydroxyl group-containing (meth) acrylate as essential components. In the present invention, N-isopropylacrylamide is used as a raw material for the acrylic resin in order to impart temperature responsiveness to the acrylic resin. As described above, when the acrylic resin exhibits temperature responsiveness, the moisture-permeable waterproof film containing the acrylic resin exhibits hydrophilicity at a low temperature range and exhibits hydrophobicity at a high temperature range. When this moisture permeable waterproof film is used, moisture is absorbed by the moisture permeable waterproof film in a low temperature range, so that the dew condensation suppressing effect and the moisture permeability measured based on the JIS L1099 B-1 method are improved. On the other hand, in the high temperature range, moisture is hardly absorbed by the moisture permeable waterproof film, and as a result, the moisture transmission rate is hardly lowered, and the moisture permeability measured based on the JIS L1099 B-1 method is improved.

In 100% by mass of the acrylic resin monomer mixture, the amount of NIPAM used is, for example, preferably 50 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 50 to 85% by mass. If the amount of NIPAM used is within the above range, the moisture-permeable waterproof film can exhibit a clear temperature response, which is preferable. In the present invention, in 100% by mass of the acrylic resin monomer mixture, NIPAM, a hydroxyl group-containing (meth) acrylate described later, and a monomer having an α, β-unsaturated ethylenic bond added as necessary Is 100% by mass.

Further, in order to modify the urethane resin with the acrylic resin (that is, to react an isocyanate group in the polyurethane resin described later or a group derived therefrom with the acrylic resin), the acrylic resin monomer mixture contains a hydroxyl group ( Contains (meth) acrylates. In the present invention, “(meth) acrylate” means methacrylate or acrylate. Examples of the hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include caprolactone-modified hydroxy (meth) acrylate, methyl α- (hydroxymethyl) acrylate, ethyl α- (hydroxymethyl) acrylate, and mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol. Of these, 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate is preferable.

The amount of the hydroxyl group-containing (meth) acrylate used in 100% by mass of the acrylic resin monomer mixture is preferably, for example, 0.5 to 5% by mass, more preferably 0.7 to 3% by mass, More preferably, it is 1 to 2.5% by mass. If the hydroxyl group-containing (meth) acrylates are within the above range, it is preferable because a sufficient amount of reaction points can be formed when reacting with the urethane resin.

The monomer mixture for acrylic resin may further contain a monomer having an α, β-unsaturated ethylenic bond other than the monomers described above, if necessary. Examples of the monomer having an α, β-unsaturated ethylenic bond include (meth) acrylic acid; (meth) acrylates; (meth) acrylamides (excluding N-isopropylacrylamide (NIPAM)). Acrylonitrile, styrene, α-methylstyrene, vinyltoluene, N-vinylacetylamide; and the like.

Examples of the (meth) acrylates include the following formula (1):

(Wherein R ¹ represents an alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and m is 0 or 1).

Examples of the alkyl group represented by R ¹ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, and a hexyl group. And linear or branched alkyl groups such as a group, octyl group, decyl group, undecyl group, dodecyl group, cetyl group and stearyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Of these, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group are preferable, and a methyl group is more preferable.

Examples of the cycloalkyl group represented by R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group. The number of constituent elements of the ring skeleton of the cycloalkyl group is preferably 3 to 15, more preferably 5 to 9, and still more preferably 6 (cyclohexyl group).

M in the (meth) acrylates may be 0 or 1, but in the present invention, acrylates in which m is 0 are particularly preferable.

In 100% by mass of the acrylic resin monomer mixture, the (meth) acrylate is preferably contained in an amount of 1 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 5 to 10%. % By mass. It is preferable to adjust the (meth) acrylates within the above range because hydrophobicity can be imparted to the acrylic resin. LCST tends to decrease as the amount of (meth) acrylates increases.

The (meth) acrylamides (excluding N-isopropylacrylamide) include N-ethylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-methoxypropylacrylamide, N-ethoxypropylacrylamide, N-isopropoxypropylacrylamide, N- Ethoxyethyl acrylamide, N- (2,2-dimethoxyethyl) -N-methyl acrylamide, N-1-methyl-2-methoxyethyl acrylamide, N-1-methoxymethylpropyl acrylate Amides, N-di (2-methoxyethyl) acrylamide, N-2-methoxyethyl-Nn-propylacrylamide, N-2-methoxyethyl-N-ethylacrylamide, N-2-methoxyethyl-N-isopropylacrylamide N-methoxyethoxypropylacrylamide, N-tetrahydrofurfurylacrylamide, N- (1,3-dioxolan-2-yl) methylacrylamide, N-methyl-N- (1,3-dioxolan-2-yl) methylacrylamide And various acrylamides such as N-cyclopropylacrylamide and N-pyrrolidinomethylacrylamide. Among them, the following formula (2):

(Wherein R ² and R ³ are the same or different and are a hydrogen atom, a linear or branched alkyl group having 1 to 15 carbon atoms, and n is 0 or 1) (meth) Acrylamides are preferred.

As the alkyl group of R ² and R ³ in the formula (2), those exemplified in the column of R ¹ can be preferably used, and the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Particularly preferred is 1 to 4. Of these, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl and sec-butyl are preferred.

Further, as the cycloalkyl group of R ² and R ³ in the formula (2), those exemplified in the column of R ¹ can be preferably used, and the number of constituent elements of the ring skeleton of the cycloalkyl group is preferably 3 to 15, The number is preferably 3 to 8, and more preferably 3 to 5.

Such (meth) acrylamides include N-tert-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N , N-dimethyl (meth) acrylamide is preferably used.

N in the (meth) acrylamides may be 0 or 1, but acrylamides in which n is 0 are particularly preferred in the present invention.

In 100% by mass of the acrylic resin monomer mixture, the (meth) acrylamide is preferably contained in an amount of 3 to 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10 to 25%. % By mass. By copolymerizing (meth) acrylamides, LCST can be easily adjusted and hydrophobicity can be imparted to the acrylic resin.

In order to produce an acrylic resin by copolymerizing the aforementioned monomers, for example, in the presence of a radical polymerization initiator, at least NIPAM and hydroxyl group-containing (meth) acrylates, and if necessary, α, β other than these It is preferable to react with a monomer having an unsaturated ethylenic bond.

Examples of the radical polymerization initiator include azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis- (4 Azo polymerization initiators such as -methoxy-2,4-dimethylvaleronitrile); organic compounds such as tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide Peroxides; persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate; hydrogen peroxide; and the like. These may be used alone or in combination of two or more.

The amount of the radical polymerization initiator used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the acrylic resin monomer mixture. If the amount of the radical polymerization initiator is within the above range, it is preferable because the molecular weight of the acrylic resin can be adjusted to an appropriate range and the reaction can sufficiently proceed.

The copolymerization reaction for producing the acrylic resin may be carried out in the absence of a solvent or in the presence of a solvent, but is preferably carried out in the presence of a solvent. Solvents that can be preferably used in the copolymerization reaction include, for example, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; N, N-dimethyl And acetamide solvents such as acetamide and N, N-diethylacetamide; The solvent may be used in an amount such that the solid content concentration in the reaction solution is 5 to 80% by mass (more preferably 40 to 70% by mass).

The reaction temperature in the copolymerization reaction is preferably 20 to 120 ° C. If the reaction temperature is too low, the reaction takes a long time, which is not preferable, and if the reaction temperature is too high, a side reaction may occur.

<Polyurethane resin>
Next, the polyurethane resin will be described. The polyurethane resin is obtained by polymerization from a monomer mixture for a polyurethane resin containing a polyol and a polyisocyanate generally used as a raw material for the polyurethane resin.

Examples of polyols include compounds having di- or higher hydroxyl groups, and these can be used alone or in combination of two or more. The polyol may be a low molecular weight product having a weight average molecular weight of less than 400 or a high molecular weight product having a weight average molecular weight of 400 to 4000.

Low molecular weight polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, hexanetriol, diglycerin, penta Examples include polyols such as erythritol and sorbitol; polyamines such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophoronediamine; aminoalcohols; and the like. These may be used alone or in combination of two or more.

Examples of the polyol having a weight average molecular weight of 400 to 4000 high molecular weight include polyether polyols, polyester polyols, polyether polyols, or polymer polyols obtained by grafting a vinyl monomer to polyester polyols.

The polyether polyol is a polyalkylene glycol obtained by addition polymerization of an alkylene oxide (ethylene oxide, propylene oxide, etc.) to an initiator having active hydrogen. Examples of the initiator include polyols, polyamines, and amino alcohols exemplified in the low molecular weight polyol column. A polyurethane resin containing a polyol as a constituent unit is preferable for a moisture-permeable and waterproof film because of its high hydrophilicity. Examples of such polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like, and polyether polyols obtained by copolymerizing these polyalkylene glycols, and these may be used alone or in combination of two or more thereof. .

The polyester polyol is obtained by dehydrating and condensing dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and trimellitic acid to the above-described low molecular weight polyol. Condensed polyester polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexamethylene adipate (PHMA); obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone to the above-mentioned low molecular weight polyols Lactone polyester polyols such as poly-ε-caprolactone (PCL); polycarbonate diols such as polyhexamethylene carbonate; and the like. These may be used alone or in combination of two or more.

On the other hand, examples of the polyisocyanate include aromatic, aliphatic and alicyclic isocyanates having di- or higher isocyanate groups. Examples of the polyisocyanate include toluene diisocyanate (2,4-TDI, 2,6-TDI, etc.), diphenylmethane diisocyanate (2,2′-MDI, 2,4′-MDI, 4,4′-MDI, etc.), Aromatic isocyanates such as naphthalene diisocyanate (1,5-NDI, etc.), xylene diisocyanate (XDI), 4,4′-diisocyanato-3,3′-dimethylbiphenyl (TODI); tetramethylene diisocyanate, hexamethylene diisocyanate (1 , 6-HDI, etc.), 1,3,6-hexamethylene triisocyanate, dodecane diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and other aliphatic isocyanates; 3-isocyanate methyl-3,3,5′-trimethyl And alicyclic isocyanates such as cyclohexyl diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylene diisocyanate, norbornene diisocyanate methyl; These can be used alone or in combination of two or more. Among these, aromatic isocyanates are preferable, and more preferably one of toluene diisocyanate and diphenylmethane diisocyanate, or both.

The method for producing the polyurethane resin is not particularly limited, and examples thereof include a one-shot method and a prepolymer method. In the present invention, since the acrylic resin having the temperature responsiveness described above is used after being reacted with the polyurethane resin, the prepolymer method is preferable. In the monomer mixture for the polyurethane prepolymer, the polyol may be used so that the number of moles of the hydroxyl group in the polyol is 0.5 to 2.5 mol with respect to 1 mol of the isocyanate group in the polyisocyanate. It is more preferable to use the polyol in a small excess so as to be 1 to 2 mol.

In the production of the prepolymer, it is also a preferred embodiment to use a solvent from the viewpoint of adjusting the viscosity and improving the emulsifying dispersibility of the prepolymer. As the solvent, it is preferable to use a solvent that is inert to isocyanate groups and that is relatively hydrophilic. Specifically, amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; carbonization such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, mineral spirit, etc. Hydrogens; alcohols such as isopropyl alcohol and tert-butyl alcohol; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, propyl acetate and propylene glycol monomethyl ether acetate; diethyl ether, cyclohexyl methyl ether, di Ethers such as butyl ether, dimethoxyethane, dioxane, tetrahydrofuran, dioxolane; methyl ethyl ketone, methyl isobutyl ketone Ketones such as cyclohexanone; and the like, may be used singly or in combination of two or more.

The temperature at the time of producing the prepolymer is not particularly limited, but is preferably 50 to 200 ° C, more preferably 60 to 120 ° C. The reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 3 hours.

In addition, a known catalyst can be used for the synthesis of the urethane prepolymer. Examples of the catalyst include monoamines such as triethylamine and N, N-dimethylcyclohexylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine Polyamines such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), cyclic diamines such as triethylenediamine; tin-based catalysts such as dibutyltin dilaurate and dibutyltin diacetate .

When the prepolymer produced by the above-described method and the polyol and / or polyisocyanate are polymerized, it is preferable to use a solvent, a catalyst, or the like detailed in the prepolymer production method.

The chain extender used for producing the above-mentioned polyurethane resin is not particularly limited, and examples thereof include water, low molecular weight polyols, polyamines, amino alcohols, and the like. As the low molecular weight polyol, the same ones as described above can be used. Examples of the polyamines include aliphatic polyamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine; aromatic polyamines such as tolylenediamine, xylylenediamine, and diaminodiphenylmethane; diaminocyclohexylmethane, piperazine, and isophoronediamine. Alicyclic polyamines; hydrazines such as hydrazine, succinic dihydrazide, adipic dihydrazide, phthalic dihydrazide, and the like. Among these, it is preferable to use ethylenediamine and / or hydrazine as a chain extender component. Examples of the alkanolamine include diethanolamine and monoethanolamine.

The acrylic resin having LCST may be added as a raw material during the production of the prepolymer, or may be added when further polymerizing the produced prepolymer and other components. It is preferred to add the resin during prepolymer production. The acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by solid content in 100% by mass of the finally obtained acrylic resin-modified urethane resin. It is good to use so that it may become mass%.

<Method for producing moisture permeable waterproof film>
The moisture-permeable waterproof film according to the present invention is formed from a resin solution containing a polyurethane resin modified with an acrylic resin. The method for producing a moisture permeable waterproof film is not particularly limited, but a resin solution containing a polyurethane resin modified with an acrylic resin is applied to a release paper and dried to be contained in the resin solution. A dry method of evaporating the organic solvent or the aqueous medium is preferable. As a method for applying the resin solution, for example, various methods such as a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Mayer bar coating method, a die coating method, and a spray coating method may be appropriately employed. If necessary, the resin solution may contain various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, and fillers. Further, an antistatic agent, a nucleating agent and the like may be blended.

The thickness of the moisture permeable waterproof film may be appropriately changed depending on the application, but is preferably 3 to 50 μm, more preferably 5 to 30 μm, and still more preferably 6 to 15 μm. If the thickness of the moisture permeable waterproof film is within the above range, it is preferable because the material can be widely applied to various uses.

<Water-permeable waterproof film>
The moisture-permeable waterproof film of the present invention has LCST as described above. LCST is preferably 0 ° C. or higher and 40 ° C. or lower, more preferably 5 ° C. or higher and 35 ° C. or lower, still more preferably 10 ° C. or higher and 35 ° C. or lower, and still more preferably 15 ° C. or higher and 30 ° C. or lower. Since the freezing point of water is 0 ° C., if the LCST is lower than 0 ° C., there is a possibility that desired effects such as a dew condensation suppressing effect cannot be sufficiently exhibited in the obtained moisture-permeable waterproof film. Moreover, when LCST exceeds 40 ° C., appearance defects due to swelling of the water-absorbed membrane surface, which is a problem in conventional moisture-permeable waterproof films, deterioration of washing durability, moisture permeability, and further deterioration due to moisture permeability There is a possibility that improvement of dripping will be insufficient. To increase the LCST, the amount of (meth) acrylamides should be reduced, and to lower the LCST, the amount of (meth) acrylamides should be increased. LCST can be measured by the method described below.
[LCST] A moisture-permeable waterproof film having a thickness of 50 μm is cut into a 5 cm square, the cut sample film is dried at 120 ° C. for 15 minutes, and the absolutely dry mass W ₀ of the sample film after drying is obtained. Next, after immersing the dried sample film for 2 minutes in ion exchange water whose water temperature is adjusted to T ° C., the mass W ₁ of the sample film immediately after being pulled up from the ion exchange water is measured (sample film). Wipe off water droplets adhering to the front and back of the filter paper). Water absorption S% at T ° C. is obtained by converting the W ₁ / W ₀ in percent. And in order to obtain | require LCST, the value of T is changed and the water absorption S% in each temperature is calculated | required. The results are plotted so that the temperature is T ° C. on the x-axis and the water absorption S% is on the y-axis, and the temperature at which the water absorption S% changes greatly is determined by looking at the produced graph. To do.

The moisture-permeable waterproof film according to the present invention has high water pressure resistance, and the water pressure resistance measured by the method described below is 50 kPa or more, and can be 100 kPa or more. The upper limit of the water pressure resistance is not particularly limited, but it is 450 kPa or less, and even if it is 400 kPa or less, there is no problem. If the water pressure resistance is too low, the film cannot maintain rigidity, and it may be difficult to apply it to clothing materials such as rain clothes and sportswear. When the water pressure resistance is too high, the texture of the film becomes hard, and it may be difficult to apply to the clothing material.
[Water-resistant pressure] A moisture-permeable waterproof film having a thickness of 10 μm is produced from a resin solution for moisture-permeable and waterproof films by a dry method and applied to a JIS L1092 7.1B method (high water pressure method). ).

The moisture-permeable waterproof film according to the present invention exhibits hydrophobicity when the temperature in the clothes is increased, and exhibits moderate moisture permeability by being difficult to swell. For example, measured according to JIS L1099 B-1 method (potassium acetate method) “B-1 moisture permeability at 43 ° C. atmosphere (measuring environment is 50 ° C. × 65% RH and water temperature in the water tank is set to 43 ° C. ) "exerts the least 20000g / m ² · 24h, can also be at least 22000g / m ² · 24h, also be at least 45500g / m ² · 24h with the presence of the polyurethane resin modified with acrylic resin Is possible. Usually, the upper limit is 50000 g / m ² · 24 h or less, and there is no problem even if it is 49000 g / m ² · 24 h or less. If the B-1 moisture permeability in a 43 ° C. atmosphere is too low, when the moisture-permeable and waterproof film of the present invention is used for clothes, the wearer of the clothes may feel uncomfortable during exercise, etc. is there. On the other hand, if the B-1 moisture permeability in a 43 ° C. atmosphere is too high, water resistance may be insufficient.

The moisture permeable waterproof film exhibits hydrophilicity when the temperature in the garment decreases, such as at the end of exercise, and exhibits effects such as suppressing condensation. For example, measured according to JIS L1099 B-1 method (potassium acetate method) “B-1 moisture permeability at 13 ° C. atmosphere (measuring environment is 20 ° C. × 65% RH, water temperature in water tank is set to 13 ° C. ) "is to demonstrate the following 16000g / m ² · 24h, it is also possible to be less than or equal to 15000g / m ² · 24h. If the B-1 moisture permeability in a 13 ° C. atmosphere is too low, the water vapor in the garment is not discharged to the outside, the amount of water vapor in the garment increases, and the temperature in the garment decreases. However, in the present invention, the lower limit is usually 12000 g / m ² · 24 h or more, and even if it is 12,500 g / m ² · 24 h or more, there is no problem.

Since the moisture-permeable waterproof film of the present invention exhibits hydrophilicity at a lower temperature range than the LCST with the LCST as a boundary, the water absorption rate is higher in this temperature range. On the other hand, since it exhibits hydrophobicity at a temperature range higher than LCST, the water absorption rate tends to be low at this temperature range. Therefore, the characteristics based on the change rate of the water absorption rate are evaluated by “change rate of the water absorption rate before and after LCST” measured by the method described below. The rate of change in water absorption before and after LCST can be 2 or more and can be 2.3 or more. Moreover, the change rate of the water absorption before and after LCST is usually 5 or less, and even if it is 4.7 or less, there is no problem. If the rate of change in water absorption before and after LCST is too low, there is a high possibility that a high water absorption rate cannot be achieved in a temperature range lower than LCST, and the dew condensation suppression effect of the moisture permeable waterproof film may not be sufficiently exhibited. . Also, if the rate of change in water absorption before and after LCST is too large, the hydrophilicity of the moisture-permeable and waterproof film will increase sharply, which may reduce the film strength.
[Change rate of water absorption rate before and after LCST] The change rate of water absorption rate before and after LCST is 10 ° C higher than the LCST-LCST. It is defined as the value divided by the rate of change in water absorption (%) between the temperatures. The method for measuring the water absorption S% is the same as the method described in the LCST column. The water absorption S _{1 at} LCST-10 (° C.) and the water absorption S ₂ at LCST (° C.) are respectively determined, and the change rate _RA of the water absorption before LCST is determined from (S ₁ -S ₂ ) / S ₁ . Further, the water absorption S ₃ at LCST + 10 (° C.) is obtained, and the change rate R _B of the water absorption after LCST is obtained from (S ₂ −S ₃ ) / S ₂ . Rate of change of the water absorption before and after the LCST is evaluated by R _A / R _B.

<Composite fabric>
The present invention also includes a composite fabric in which the moisture-permeable and waterproof film is laminated on a base fabric. By making the composite fabric in this way, in addition to the characteristics of the base fabric itself, moisture permeability and waterproofness were imparted, and it was particularly excellent for various apparel applications such as rain (snow), sports, outdoor use, work use, etc. It is preferable because a dough can be obtained.

Examples of the base fabric of the composite fabric include woven fabric, knitted fabric, non-woven fabric, lace, and net. The woven structure of the woven fabric is not particularly limited, and examples thereof include plain weave, twill weave, satin weave, and dobby weave. The knitting structure of the knitted fabric includes, for example, weft knitting such as flat knitting, rib knitting, double-sided knitting and pearl knitting; warp knitting such as tricot knitting and russell; round knitting such as tengu, smooth, milling, picket and blister; Is mentioned. Furthermore, examples of the nonwoven fabric include wet nonwoven fabrics such as chemical bonds, thermal bonds, and spunlaces; dry nonwoven fabrics such as chemical bonds, thermal bonds, spunlaces, and needle punches; and spunbond nonwoven fabrics. Since the moisture-permeable waterproof film of the present invention has an appropriate strength, it is possible to produce a fabric that is not easily torn and has excellent wear resistance. Further, when the moisture permeable waterproof film and the knitted fabric are combined, a knitted fabric excellent in moisture permeable and waterproof properties can be produced without impairing the unique stretchability and soft texture of the knitted fabric.

The base fabric preferably contains various fibers. Examples of the fibers include polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; polyamide fibers such as nylon 6 and nylon 66; polyimide fibers. Acrylic fibers; polyolefin fibers such as polypropylene and polyethylene; synthetic fibers such as polyurethane fibers; natural fibers such as cotton and hemp; regenerated fibers such as rayon; semisynthetic fibers such as acetate fibers; These fibers may be used alone or in combination. In particular, in order to improve the waterproof performance of the composite fabric, it is preferable that the base fabric mainly contains synthetic fibers. Specifically, it is preferable that 50% by mass or more of the synthetic fibers are contained in 100% by mass of the base fabric. More preferably, it is 75 mass% or more, More preferably, it is 85 mass% or more, Most preferably, it is 95 mass% or more. The upper limit is preferably 100% by mass, but even if it is 97% by mass or less, it is acceptable.

The fibers constituting the base fabric include, for example, at least one inorganic fine particle selected from titanium oxide, zinc oxide, alumina (aluminum oxide), magnesium oxide, barium sulfate, talc, kaolin, calcium carbonate, sodium carbonate, and the like. Also good. As the inorganic fine particles, titanium oxide is particularly preferable. The fiber may be a semidal containing 0.01 to 1.2% by mass of inorganic fine particles in 100% of the fiber, or a fuller containing 1.2 to 7% by mass of the inorganic fine particles. When the upper limit is exceeded, the yarn-making property is lowered, and it may be difficult to stably produce a uniform spun yarn.

The thickness of the fibers constituting the base fabric and the number of filaments may be appropriately adjusted according to the intended use of the resulting fabric, and the multifilament used for the warp of the plain woven fabric preferably has a fineness of 50 to 280 dtex, more preferably 60 ~ 200 dtex. Further, the number of monofilaments in one multifilament is not particularly limited, and is preferably 150 to 500, for example, and more preferably 200 to 400.

The base fabric can be subjected to water-repellent finishing, soft finishing, resin processing, and antistatic processing for adjusting the texture and the strength of the fabric as necessary. These processes may be performed before compounding with the moisture permeable waterproof film, or may be performed after combining the moisture permeable waterproof film and the fabric.

The water repellent used in the water repellent process may be a general fiber water repellent, such as a silicone water repellent, a fluorine water repellent composed of a polymer having a perfluoroalkyl group, and a paraffin water repellent. An agent is preferably used. As a water repellent processing method, a general method such as a padding method, a spray method, printing, coating, or a gravure method can be used. In the present invention, it is particularly preferable to apply a water-repellent finish to the fabric because the waterproof performance of the fabric is improved and the wearing comfort is enhanced even under high humidity such as rainy weather.

Further, examples of the softener used for the soft finish include amino-modified silicone, polyethylene-based, polyester-based, paraffin-based softeners, and the like. Moreover, the flexible process using these and a silicone process can be performed as a post-process for finishing.

As a method of combining the moisture permeable waterproof film and the base fabric, a method of bonding the moisture permeable waterproof film and the base fabric to each other through an adhesive; a method of joining by heat treatment; a method of joining by stitching; Is mentioned. As said adhesive agent, if it is an adhesive agent used for joining of a general purpose film and cloth, it can use widely, For example, a polyurethane-type adhesive agent etc. are preferable. In addition, when bonding both with an adhesive agent, it is good to laminate and fix a base fabric, for example, after printing an adhesive agent on a moisture-permeable waterproof film in a linear form or a dot form. Moreover, when apply | coating an adhesive agent, it is good to apply | coat to the one part or the whole surface of a moisture-permeable waterproof film uniformly by a coating method, a gravure method, etc., and to adhere | attach with a base fabric. At this time, pressure may be applied to the laminate of the fabric and the moisture-permeable waterproof film, and both may be pressure bonded.

When preparing a fabric obtained by joining the moisture permeable waterproof film and the base fabric according to the present invention as clothing, the moisture permeable waterproof film is directed to the skin side of the wearer.

Also, it is possible to laminate a protective layer on the moisture permeable waterproof film side surface of the composite fabric of the moisture permeable waterproof film and the base fabric. By laminating the protective layer, the practical durability of the composite fabric is improved, and stickiness during sweating due to contact between the skin and the moisture-permeable waterproof film can be improved. Moreover, if a protective layer is laminated | stacked, it can also be expected that the tear strength and breaking strength of the composite fabric are improved. Examples of the method of bonding the protective layer include a method of bonding the protective layer and the moisture permeable waterproof film via an adhesive layer, and the kind and application method of the adhesive are applied by attaching the moisture permeable waterproof film and the base fabric described above. It is the same as the method of matching. However, when bonding a protective layer through an adhesive, it is better that the adhesive is not applied to the entire surface of the protective layer. This is because if the adhesive is applied to the entire surface of the protective layer, the moisture permeability of the composite fabric decreases, and the wearer may feel sticky when sweating. Moreover, since the design of the back surface of the composite fabric can be improved by not applying the adhesive to the entire surface of the protective layer, the appearance is improved.

Examples of the protective layer include woven fabrics, knitted fabrics, non-woven fabrics, laces, nets and the like, as in the case of the base fabric. Among them, at least one selected from woven fabrics, circular knitted fabrics, warp knitted fabrics and non-woven fabrics is preferable. These protective layers may be used alone or in combination of two or more. Moreover, as a fiber of a protective layer, since it is excellent in durability, a synthetic fiber like a polyester fiber (for example, polyethylene terephthalate) and a polyamide fiber (for example, nylon 6, nylon 66) is preferable.

The composite fabric made by combining the moisture permeable waterproof film and the base fabric manufactured by the method described above is used for rain (snow) clothing such as rain clothing; sports clothing such as golf, skiing and snowboarding; It can be preferably used as a clothing material such as clothing; work clothing for workers working in high-temperature environments, humid environments, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

<Water pressure resistance>
The water pressure resistance of the moisture permeable waterproof film was obtained by manufacturing a moisture permeable waterproof film having a thickness of 10 μm by a dry method from the resin solution for moisture permeable waterproof film manufactured in the column of Examples / Comparative Examples. Measured according to JIS L1092 7.1B method (high water pressure method).

<Moisture permeability>
The measurement is performed according to JIS L1099 B-1 method (potassium acetate method) using a moisture-permeable waterproof film having a thickness of 10 μm. “B-1 moisture permeability at 13 ° C. atmosphere” is measured by setting the measurement environment to 20 ° C. × 65% RH and the water temperature in the water tank to 13 ° C. “B-1 moisture permeability at 43 ° C. atmosphere” is measured by setting the measurement environment to 50 ° C. × 65% RH and the water temperature in the water tank to 43 ° C.

<Lower critical eutectic temperature (LCST)>
First, a moisture permeable waterproof film having a thickness of 50 μm is produced by a dry method using the resin solution for moisture permeable waterproof film prepared in Examples and Comparative Examples. The manufactured moisture permeable waterproof film is cut into 5 cm square, the cut sample film is dried at 120 ° C. for 15 minutes, and the absolutely dry mass W ₀ of the dried sample film is obtained. Next, after immersing the dried sample film for 2 minutes in ion exchange water whose water temperature is adjusted to T ° C., the mass W ₁ of the sample film immediately after being pulled up from the ion exchange water is measured (sample film). Wipe off water droplets adhering to the front and back of the filter paper). The water absorption S% at T ° C. is obtained by converting W ₁ / W ₀ into percentage. And in order to obtain | require LCST, the value of T is changed and the water absorption S% in each temperature is calculated | required. The results are plotted so that the temperature is T ° C. on the x-axis and the water absorption S% is on the y-axis, and the temperature at which the water absorption S% changes greatly is determined by looking at the produced graph. To do.

<Change rate of water absorption before and after LCST>
The method for measuring the water absorption S% is the same as the method described in the LCST column. The water absorption S _{1 at} LCST-10 (° C.) and the water absorption S ₂ at LCST (° C.) are respectively determined, and the change rate _RA of the water absorption before LCST is determined from (S ₁ -S ₂ ) / S ₁ . Further, the water absorption S ₃ at LCST + 10 (° C.) is obtained, and the change rate R _B of the water absorption after LCST is obtained from (S ₂ −S ₃ ) / S ₂ . Rate of change of the water absorption before and after the LCST is evaluated by R _A / R _B.

<Judgment of quality as clothing material>
Using the composite fabrics prepared in Examples and Comparative Examples, repeated washing (20 times) and hanging drying were performed according to JIS L0217 103 method, and the appearance quality of the film surface was confirmed. If there is a defect (breaking, etc.) on the film surface, it is judged as “bad”, and there is no defect on the film surface. A beautiful item was defined as “good”.

Example 1
158 parts of isopropyl acrylamide (NIPAM), 13 parts of methyl acrylate (MA), 24 parts of tert-butyl acrylamide (TBAA), 3 parts of 2-hydroxyethyl acrylate (HEA), 5 parts of azobisisobutyronitrile (AIBN) Then, solution polymerization was performed in a mixed solution of 300 parts of DMF to produce an acrylic resin (AC-1) having a hydroxyl group in the molecule.

(1) Production of prepolymer solution 600 parts of polyethylene glycol (PEG) having a weight average molecular weight of 2,000, 532 parts of acrylic resin (AC-1) having a hydroxyl group in the molecule, and 535 parts of dimethylformamide (DMF) under a nitrogen stream Then, 31 parts of 4,4′-diphenylmethane diisocyanate (MDI) and 5.2 parts of 2,6-triene diisocyanate (2,6-TDI) are added, and the mixture is heated at 75 ° C. for about 1 hour. A polymer solution was obtained.

(2) Manufacture of resin solution for moisture permeable waterproof film Next, 567 parts of DMF and 105 parts of ethylene glycol (EG) are added to the prepolymer solution manufactured in step (1) and mixed uniformly, and then 463 parts of MDI is added. It was. In addition to the thickening of the polymer, 711 parts of DMF and 1185 parts of methyl ethyl ketone (MEK) were added and stirred while diluting to increase the viscosity until the viscosity at 25 ° C. reached 70000 mPa · s, and then the reaction was stopped.

(3) Manufacture of moisture-permeable and waterproof film From the resin solution for moisture-permeable and waterproof films obtained as described above, a moisture-permeable and waterproof film was prepared by a dry method so as to have a thickness of 50 μm. When the LCST was measured for the produced moisture-permeable waterproof film, the LCST was 25 ° C., and the value obtained by dividing the change in water absorption between 15 and 25 ° C. by the change in water absorption between 25 and 35 ° C. was 2.5. It became.

(4) Manufacture of base fabric and composite fabric Next, from the resin solution for moisture permeable waterproof film produced in the step (2), two moisture permeable waterproof films were prepared by a dry method so as to have a thickness of 10 μm. . In addition, a plain-textured fabric was manufactured using polyester semi-dal yarn (78 dtex, 216 filament) as warp and polyester semi-dal yarn (156 dtex, 432 filament) as weft. This fabric was subjected to general dyeing and water-repellent finishing as a final finish. The produced woven fabric had a warp density of 140 yarns / inch, a weft density of 83 yarns / inch, and a basis weight of 116 g / m ² . A moisture curable polyurethane adhesive was arranged with 16 mesh dots on one moisture permeable waterproof film having a thickness of 10 μm, and a plain fabric prepared thereon was bonded to produce a composite fabric.

Example 2
100 parts of isopropyl acrylamide (NIPAM), 19 parts of diethyl acrylamide (DEAA), 26 parts of methyl acrylate (MA), 50 parts of tert-butyl acrylamide (TBAA), 3 parts of 2-hydroxypropyl acrylate (HEA), azobisisobuty An acrylic resin (AC-2) having a hydroxyl group was produced by solution polymerization of 5 parts of ronitrile (AIBN) in a mixed solution of 300 parts of DMF.

(1) PEG 550 parts with a weight average molecular weight of 2000, 50 parts of polytetramethylene glycol (PTMG) with a weight average molecular weight of 2000, 532 parts of an acrylic resin (AC-2) having a hydroxyl group in the molecule, and 535 parts of DMF under a nitrogen stream Then, 38 parts of MDI was added and heated at 75 ° C. for about 1 hour to prepare a prepolymer solution.

(2) Next, 567 parts of DMF and 105 parts of EG were added to the prepolymer solution produced in the step (1) and mixed uniformly, and then 463 parts of MDI was added. In addition to the thickening of the polymer, 711 parts of DMF and 1185 parts of MEK were added and stirring was continued while diluting to increase the viscosity until the viscosity at 25 ° C. reached 70000 mPa · s, and then the reaction was stopped.

(3) A moisture permeable waterproof film was prepared from the resin solution for a moisture permeable waterproof film thus obtained so as to have a thickness of 50 μm by a dry method. When the LCST was measured for the produced moisture-permeable waterproof film, the LCST was 20 ° C., and the value obtained by dividing the change in water absorption between 10 and 20 ° C. by the change in water absorption between 20 and 30 ° C. was 4. 0.

(4) Next, two moisture permeable waterproof films were produced from the resin solution for moisture permeable waterproof film produced in the step (2) so as to have a thickness of 10 μm by a dry method. A plain-textured fabric was produced in the same manner as in Example 1. A moisture-curable polyurethane-based adhesive was arranged with 16 mesh dots on one piece of a moisture-permeable waterproof film having a thickness of 10 μm, and was produced thereon. A plain fabric was laminated to produce a composite fabric.

Comparative Example 1
(1) After 600 parts of PEG having a weight average molecular weight of 2000 and 641 parts of DMF were uniformly mixed under a nitrogen stream, 38 parts of MDI was added and heated at 75 ° C. for about 1 hour to prepare a prepolymer solution. Next, 567 parts of DMF and 105 parts of EG were added to the prepared prepolymer solution and mixed uniformly, and then 463 parts of MDI was added to increase the viscosity. Further, 604 parts of DMF and 1008 parts of MEK were added together with the thickening of the polymer, and while diluting, the viscosity at 25 ° C. was increased to 70000 mPa · s, and the reaction was stopped.

(2) A moisture permeable waterproof film was prepared from the resin solution for a moisture permeable waterproof film thus obtained so as to have a thickness of 50 μm by a dry method. Although LCST was measured about the manufactured moisture-permeable waterproof film, LCST was not able to be confirmed.

(3) Next, two moisture permeable waterproof films were produced from the resin solution for the moisture permeable waterproof film produced in the step (2) so as to have a thickness of 10 μm by a dry method. A plain-textured fabric was produced in the same manner as in Example 1. A moisture-curable polyurethane-based adhesive was arranged with 16 mesh dots on one piece of a moisture-permeable waterproof film having a thickness of 10 μm, and was produced thereon. A plain fabric was laminated to produce a composite fabric.

Comparative Example 2
(1) After 600 parts of PEG having a weight average molecular weight of 2000 and 641 parts of DMF were uniformly mixed under a nitrogen stream, 38 parts of MDI was added and heated at 75 ° C. for about 1 hour to prepare a prepolymer solution.

(2) Next, 567 parts of DMF and 105 parts of EG were added to the prepolymer solution produced in the step (1) and mixed uniformly, and then 463 parts of MDI was added to increase the viscosity. Further, 604 parts of DMF and 1008 parts of MEK were added together with the thickening of the polymer, and while diluting, the viscosity at 25 ° C. was increased to 70000 mPa · s, and the reaction was stopped. Thereafter, 150 parts of a solution of acrylonitrile styrene copolymer resin dissolved in DMF to a solid content concentration of 30% was added to 850 parts of the produced resin solution to obtain a solution for moisture permeable waterproof film.

(3) A moisture permeable waterproof film was prepared from the resin solution for a moisture permeable waterproof film thus obtained so as to have a thickness of 50 μm by a dry method. Although LCST was measured about the manufactured moisture-permeable waterproof film, LCST was not able to be confirmed.

Comparative Example 3
79 parts isopropylacrylamide (NIPAM), 16 parts methyl acrylate (MA), 77 parts tert-butylacrylamide (TBAA), 3 parts 2-hydroxypropyl acrylate (HEA), 5 parts azobisisobutyronitrile (AIBN) Then, solution polymerization was performed in a mixed solution of 300 parts of DMF to produce an acrylic resin (AC-3) having a hydroxyl group in the molecule.

(1) 600 parts of PEG having a weight average molecular weight of 2000, 532 parts of an acrylic resin (AC-3) having a hydroxyl group in the molecule, and 535 parts of DMF were uniformly mixed under a nitrogen stream, and then 38 parts of MDI was added, and 75 ° C. For about 1 hour to prepare a prepolymer solution.

(3) A moisture permeable waterproof film was prepared from the resin solution for a moisture permeable waterproof film thus obtained so as to have a thickness of 50 μm by a dry method. When LCST was measured about the manufactured moisture-permeable waterproof film, LCST was 0 degrees C or less, and it was not able to confirm.

Comparative Example 4
(1) 600 parts of PEG having a weight average molecular weight of 2000, 177 parts of an acrylic resin (AC-1) having a hydroxyl group in the molecule, and 641 parts of DMF were mixed uniformly under a nitrogen stream, and then 38 parts of MDI was added, and 75 ° C. For about 1 hour to prepare a prepolymer solution.

(2) Next, 567 parts of DMF and 105 parts of EG were added to the prepolymer solution produced in the step (1) and mixed uniformly, and then 463 parts of MDI was added to increase the viscosity. Moreover, DMF711 part and MEK1185 part were added with the thickening of the polymer, the viscosity in 25 degreeC increased to 70000 mPa * s, diluting, and reaction was stopped.

(3) A moisture permeable waterproof film was prepared from the resin solution for a moisture permeable waterproof film thus obtained so as to have a thickness of 50 μm by a dry method. When the LCST was measured for the produced moisture-permeable waterproof film, the LCST was 25 ° C., and the value obtained by dividing the change in water absorption between 15 and 25 ° C. by the change in water absorption between 25 and 35 ° C. was 1. It became 5.

FIG. 1 shows a graph for LCST measurement in Examples 1-2 and Comparative Examples 1-3. As shown in FIG. 1, it can be seen that the water absorption rate of the moisture-permeable waterproof film produced in Example 1 changes greatly in the vicinity of 25 ° C. Moreover, since the water absorption rate of the moisture permeable waterproof film produced in Example 2 also changed greatly around 20 ° C., the LCST of Example 1 was set to 25 ° C., and the LCST of Example 2 was set to 20 ° C. On the other hand, the moisture-permeable and waterproof films produced in Comparative Examples 1 and 2 did not contain a polyurethane resin modified with an acrylic resin, so there was no change in water absorption rate, and LCST was not measured. Furthermore, although the moisture-permeable waterproof film produced in Comparative Example 3 includes a polyurethane resin modified with an acrylic resin, the set LCST is considered to be lower than 0 ° C., and consequently, the water absorption rate with respect to water. LCST was set to 0 ° C. because no change point was observed.

The moisture permeable waterproof film according to the present invention is used for developing both hydrophilicity and hydrophobicity depending on temperature, for example, rain (snow) clothing such as rain clothing; sports clothing such as golf, skiing and snowboarding; It can be preferably used as a film for clothing materials such as outdoor clothing such as mountain climbing; work clothing for workers working in high-temperature environments, humid environments, and the like.

Claims

A moisture-permeable waterproof film comprising a polyurethane resin modified with an acrylic resin and having a LCST (lower critical solution temperature).
The moisture permeable waterproof film according to claim 1, wherein the moisture permeable waterproof film measured by the method described below has an LCST of 0 ° C or higher and 40 ° C or lower, and the moisture permeable waterproof film does not exhibit water solubility even at LCST or lower.
[LCST] A moisture-permeable waterproof film having a thickness of 50 μm is cut into a 5 cm square, the cut sample film is dried at 120 ° C. for 15 minutes, and the absolutely dry mass W 0 of the sample film after drying is obtained. Next, after immersing the dried sample film for 2 minutes in ion exchange water whose water temperature is adjusted to T ° C., the mass W 1 of the sample film immediately after being pulled up from the ion exchange water is measured (sample film). Wipe off water droplets adhering to the front and back of the filter paper). The water absorption S% at T ° C. is obtained by converting W 1 / W 0 into percentage. And in order to obtain | require LCST, the value of T is changed and the water absorption S% in each temperature is calculated | required. The results are plotted so that the temperature is T ° C. on the x-axis and the water absorption S% is on the y-axis, and the temperature at which the water absorption S% changes greatly by looking at the produced graph is the LCST of the moisture-permeable waterproof film. .
The acrylic resin is
The moisture-permeable and waterproof film according to claim 1 or 2, which is obtained by polymerization from a monomer mixture for acrylic resin containing N-isopropylacrylamide and hydroxyl group-containing (meth) acrylate as essential components.
The moisture-permeable waterproof film according to claim 3, wherein the monomer mixture further contains a monomer having an α, β-unsaturated ethylenic bond.
The moisture permeable waterproof film according to any one of claims 1 to 4, wherein the polyol constituting the polyurethane resin contains a polyether polyol.
The water pressure resistance measured by the method described below is 50 kPa or more and 450 kPa or less,
About moisture permeability measured by the method described below,
43 ° C. B-1 moisture permeability atmosphere is 20000g / m 2 · 24h or more 50000 g / m and a 2 · 24h or less,
13 ° C. B-1 moisture permeability atmosphere is 12000g / m 2 · 24h or more 16000 g / m and a 2 · 24h or less,
The moisture-permeable and waterproof film according to any one of claims 1 to 5, wherein the rate of change in water absorption before and after LCST measured by the method described below is 2 or more and 5 or less.
[Water-resistant pressure] A moisture-permeable waterproof film having a thickness of 10 μm is produced from a resin solution for moisture-permeable and waterproof films by a dry method and applied to a JIS L1092 7.1B method (high water pressure method). ).
[Moisture permeability] Measured according to JIS L1099 B-1 method (potassium acetate method) using a moisture permeable waterproof film having a thickness of 10 μm. “B-1 moisture permeability at 13 ° C. atmosphere” is measured by setting the measurement environment to 20 ° C. × 65% RH and the water temperature in the water tank to 13 ° C. “B-1 moisture permeability at 43 ° C. atmosphere” is measured by setting the measurement environment to 50 ° C. × 65% RH and the water temperature in the water tank to 43 ° C.
[Change rate of water absorption rate before and after LCST] The change rate of water absorption rate before and after LCST is 10 ° C higher than the LCST-LCST. It is obtained by dividing by the rate of change in water absorption (%) between the temperatures.
A composite fabric characterized by laminating the moisture-permeable and waterproof film according to any one of claims 1 to 6 on a base fabric.