JP2639780B2 - Hand bag - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gloves having the property of shrinking by moisture or moisture.

[0002]

2. Description of the Related Art Conventionally, gloves that shrink by heat or hot water (JP-A-60-259602, JP-A-63-115019, JP-A-03-30215) have conventionally been used as shrinkable gloves.
And the like) have been proposed.

[0003]

However, the above-mentioned gloves may not be sufficiently shrunk at a temperature near room temperature (10 to 35 ° C.). However, in a place where the temperature exceeds 40 ° C., it easily shrinks and its storage is naturally limited. There was a problem that it was not practical. .

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, the glass transition point (Tg) is lowered by 1 ° C. or more by absorbing moisture, and the specific range is reduced. The above problems can be easily solved by using gloves made of a resin adjusted so as to have both the melting temperature and the heat of fusion, and shrinking at least 10% or more on a length basis at 0 to 35 ° C. Was found to be extremely high, and reached the present invention. That is, the present invention provides the following (1)
A glove comprising a stretch-formed product of the resin (A) adjusted to have the properties of (2) and (2), and shrinking by 10% or more on a length basis by moisture at a temperature of 0 to 35 ° C. . (1) The glass transition temperature is lowered by absorbing moisture. (2) a melting temperature of 80 ° C. or higher and a heat of fusion of 1 to 80 k;
J / kg.

The resin (A) used in the present invention is selected, for example, from the following compositions (X1) to (X6), and has a melting temperature of 80 ° C. or more and a heat of fusion of 1 to 80 kJ /.
and those adjusted so that the glass transition temperature is lowered by 1 ° C. or more depending on the weight and moisture. (X1) graft of hydrophilic resin and thermoplastic resin and / or
Or a stretch-formed product from a block copolymer; a stretched film from a graft copolymer of a starch derivative and polymethyl acrylate (US Pat. No. 4,839,450); a graft copolymer of a cellulose-based polysaccharide or the like and a thermoplastic resin Stretched film (JP-A-03-177431 and the like), stretched film from a graft copolymer of a hydrophilic synthetic resin and a thermoplastic resin (JP-A-03-37233 and the like),
Stretched film from a block copolymer of a hydrophilic synthetic resin and a thermoplastic resin (Japanese Patent Laid-Open No. 03-39331, etc.)
etc. (X2) A stretch molded product from a mixture of a hydrophilic synthetic resin and a thermoplastic resin; (X3) Stretch-formed product from hydrolyzate of vinyl ester (co) polymer; stretched film from polyvinyl alcohol having a saponification degree of 98 mol% or more (Japanese Patent Laid-Open No. 57-16061
No. 5), a stretched film from a vinyl ester homopolymer [a stretched film from a partially hydrolyzed product of polyvinyl acetate (hydrolysis rate: 0.1 to 75 mol%), etc.], and a vinyl ester copolymer [Stretched film from a partially hydrolyzed product of a copolymer of vinyl acetate and vinyl formate (hydrolysis rate: 0.1 to 75 mol%)] and the like. (X4) a stretch molded product comprising a random copolymer containing a vinyl ester and / or an alkyl (meth) acrylate in a constituent unit; for example, a polymerizable monomer selected from a vinyl ester compound and / or an alkyl (meth) acrylate ( X1) a stretched film from a random copolymer composed of units and a polymerizable monomer (X2) unit selected from the following a to e. a. Vinyl carboxylic acid, anhydride or monovalent salt thereof b. Vinyl sulfonic acid or its monovalent salt c. Hydroxyalkyl (meth) acrylate d. Allyl alcohol e. Polyhydric alcohol monoallyl ether f. Stretch-molded product composed of polyoxyethylene mono (meth) acrylate (X5) polyethylene oxide For example, stretch-molded product composed of cross-linked polyalkylene oxide irradiated with ionizing radiation (JP-A-05-42600)
No., etc.). (X6) Copolymer of olefin and polymerizable monomer having hydrophilic group and / or modified product thereof ((partial) hydrolyzate, (partial) etherified product, (partial) esterified product, (partial) Urethane compounds, (partially) alkoxylated compounds,
(Partial) acetalized compound, (partial) aminated compound, (partial) amidated compound, polymer reactant, etc.];
one or more copolymers with m and / or modified products thereof. g. Vinyl esters and / or their hydrolysates Vinyl aliphatic organic acid ester monomers (vinyl formate, vinyl acetate, vinyl n-propionate, vinyl n-butyrate, vinyl versatate, vinyl hydroxyacetate, vinyl hydroxybutyrate, etc.) And / or a (co) polymer comprising at least one vinyl aromatic organic acid ester monomer (eg, vinyl benzoate, vinyl p-methylbenzoate) and / or a hydrolyzate thereof. h. Vinyl carboxylic acid, anhydride or monovalent salt thereof (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or a monovalent salt thereof [alkali metal (sodium, potassium, etc.) salt , Ammonium salts, amine (monomethylamine, dimethylamine, trimethylamine, triethanolamine) salts and the like]. i. Vinyl sulfonic acid or its monovalent salt [alkali metal (sodium, potassium, etc.) salt, ammonium salt,
Amine (monomethylamine, dimethylamine, trimethylamine, triethanolamine) salts and the like]. j. Hydroxyalkyl acrylate Hydroxyethyl (meth) acrylate, hydroxybutyl acrylate and the like. k. Allyl alcohol. l. Polyhydric alcohol monoallyl ether Ethylene glycol monoallyl ether, glycerin monoallyl ether and the like. m. Vinyl halide vinyl chloride, vinylidene chloride, etc. (X1) to (X4), (X
6) may be appropriately cross-linked as long as its contractility is not impaired.

Of these, preferred are (X1)
It has a composition of (X2) and (X6), and particularly preferably has a composition of (X6).

In the present invention, the resin (A) has a functional group in the resin which is appropriately modified [hydrolysis, etherification, esterification,
Cyanation, urethanization, acetalization, amination, amidation, halogenation, sulfonation, acylation, oxidation, reduction, partial modification with a coupling agent, etc.].

Specific examples of the modification include the following methods. Hydrolysis; (K1) A resin (A) having a functional group such as an organic acid ester group, a sulfate ester group, a phosphate ester group, an ether group, an amide group and an acid catalyst (hydrochloric acid, sulfuric acid, organic acid, etc.) were used. Hydrolysis. (K2) Hydrolysis of a resin (A) having a functional group such as an ester group or an amide group with a base catalyst (eg, an alkali metal hydroxide, an alkaline earth metal hydroxide, an ammonium salt, an amine salt, etc.). Etherification; (L1) The resin (A) having an alcoholic hydroxyl group is converted to an alkali metal alkoxide with an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.), and then an alkyl halide (methyl iodide, Etherification to react with ethyl bromide. (L2) Resin having halogenated alkyl group (A) and alkali metal alkoxide (sodium methoxide, etc.)
Etherification by the reaction of (L3) Etherification by a reaction between a resin (A) having active hydrogen and an alkylene oxide (such as ethylene oxide or propylene oxide). Esterification; (M1) Hydroxyl-containing resin (A) and organic acid [formic acid, (anhydrous) acetic acid, (anhydrous) phthalic acid, (anhydrous)
Esterification by reaction with maleic acid, monochloroacetic acid, (benzoic anhydride), etc.), acid halides (acetic chloride, benzyl chloride) and the like. (M2) Resin (A) having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group and an alcohol (methanol, ethanol, isopropanol, ethylene glycol, glycerin, alkylene oxide products (polyethylene glycol, polypropylene glycol, ethylene oxide of polysaccharide) Esterification by reaction with an adduct, etc. Urethane formation; (N1) (resin (A) having a hydroxyl group and isocyanates [monoisocyanate (methyl isocyanate, butyl isocyanate, phenyl isocyanate, etc.), polyisocyanate) Reaction with isocyanates (2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, tridendiisocyanate, hexamethylene diisocyanate, and derivatives thereof) Urethanization. (N2) resin having hydroxyl group (A) and ureas with (urea, N
Urea by reaction with ethyl urea and the like. Acetalization: (O1) Acetalization by the reaction of a resin (A) having a hydroxyl group with an aldehyde (formaldehyde, n-butyraldehyde, benzaldehyde, etc.). (O2) A resin (A) having an aldehyde group and an organic substance [alcohols (methanol, ethanol, isopropanol, ethylene glycol, glycerin, alkylene oxide products (polyethylene glycol, polypropylene glycol, ethylene oxide adducts of polysaccharides, etc.)) Acetalization by reaction, etc. Amination; (P1) Resin containing nitro group (A)
With a metal catalyst (platinum, tin, etc.). (P2) Amination by reaction between the resin (A) having an alkyl halide moiety and ammonia. (P3) Amination by reaction of resin (A) having a carbonyl group with ammonia or amines. (P4) Amination of the resin (A) having a nitrile group by a reduction reaction and the like. Amidation; (Q1) Amidation by the reaction between resin (A) having an amino group and an acid halide (acetyl chloride, benzyl chloride, etc.). (Q2) Amidation or the like by reaction of a resin (A) having an aromatic amine group with an acid anhydride (such as acetic anhydride). Halogenation; (R1) Halogenation by the reaction of a resin (A) having a hydroxyl group with hydrogen halide (hydrogen iodide, hydrogen bromide, hydrogen chloride, etc.). (R2) Halogenation by reaction of a resin (A) having a hydroxyl group with phosphorus trihalide (phosphorus trichloride, phosphorus tribromide, etc.). (R3) Halogenation by reaction of a resin (A) having a hydroxyl group with thionyl chloride. Sulfonation; (S1) Sulfonation by reaction between resin (A) having an aromatic ring and sulfuric acid. Acylation; (T1) Acylation by reaction of a resin (A) having active hydrogen with an acid halide. Oxidation: (U1) Oxidation by reaction of the resin (A) with various oxidizing agents (ozone, oxygen, hypohalite, permanganate, dichromate, etc.). Reduction; (V1) Reduction by reaction of resin (A) with various reducing agents (hydrogen, alkali metal, hydrogen peroxide, sodium borohydride, lithium aluminum hydride, etc.). (W1) Modification by reaction between resin (A) and silane coupling agent (tetraalkoxysilane, monoalkyl trialkoxylan, dialkylalkoxysilane, trialkylmonoalkoxysilane, etc.). (W2) Modification by reaction between resin (A) and alkoxyaluminates. (W3) Modification by reaction between resin (A) and alkoxy titanates.

In the resin (A), plasticizers, foaming agents, lubricants, surfactants, easily decomposable additives, antistatic agents, coloring agents, fillers, inorganic substances (silica, zeolite) may be used as extenders or additives as necessary. , Activated carbon, far-infrared radiation ceramics, etc.), water absorbent resin, deodorant, fragrance, medicinal ingredients,
It may contain a fungicide, a fungicide, and the like.

In the present invention, the resin (A) is adjusted so that the glass transition temperature (Tg) is lowered by 1 ° C. or more by contact with moisture. The degree of decrease in Tg is
It is usually 1 to 300 ° C, preferably 5 to 200 ° C. T
If the degree of decrease in g is less than 1 ° C., the shrinkage due to moisture will decrease, and if it exceeds 300 ° C., the properties of the molded article will change drastically and greatly, which will hinder the operation.

The melting temperature of the resin (A) is usually 80 ° C.
That is all. If the melting temperature is lower than 80 ° C., shrinkage easily occurs in response to only the temperature, which may hinder the operation, which is not preferable. The melting temperature can be appropriately adjusted as needed by a method of adjusting the type and amount of the polymerizable monomer; a method of appropriately modifying a functional group in a resin by a chemical treatment or a physical treatment; and the like.

Further, the heat of fusion of the resin (A) is usually 1 to 8
0 kJ / kg, preferably 3 to 50 kJ / kg.
If the heat of fusion is less than 1 kJ / kg, it will shrink in response to temperature only when exposed to a temperature of about 30 to 80 ° C.
It is not preferable because the use may not be sufficient at the time of use. On the other hand, if the heat of fusion exceeds 80 KJ / Kg, the shrinkage performance due to moisture may be poor, which is not preferable.

In the present invention, in order to adjust the Tg to decrease by 1 ° C. or more due to absorption of moisture, for example, the ratio of the hydrophilic group in the resin (A) may be adjusted. The degree of the adjustment varies depending on the composition of the resin (A). For example, when the resin (A) is made of an ethylene / vinyl alcohol copolymer, if the portion derived from vinyl alcohol is at least 10 mol%, It is enough.

On the other hand, in order to adjust the melting temperature and the heat of fusion to desired ranges, the ratio of the amorphous portion to the crystalline portion in the resin (A) may be adjusted. The adjustment method and the degree of adjustment vary depending on the composition of the resin (A). For example, when the resin (A) is made of a copolymer of ethylene / vinyl alcohol, the alcohol portion in the resin is partially modified (esterified). , Acetalization, urethanization, etherification, etc.), the melting temperature and heat of fusion can be adjusted to desired ranges.

In the present invention, the melting temperature, the glass transition temperature and the heat of fusion are JIS-K7121 respectively.
And the melting temperature, glass transition temperature, and first order transition heat associated with crystal melting measured in accordance with JIS-K7122.

The method for producing the gloves of the present invention is not particularly limited. For example, (Y1) a method of preparing a stretched film of the resin (A), stacking the two films and welding and cutting them into a bill, (Y2) ) By immersing a handprint mold in a solution in which the resin (A) is dissolved or an emulsion of the resin (A), or by applying a solution or an emulsion to the handprint mold surface and then drying the mold surface After preparing an unstretched glove, the glove of the present invention can be easily formed by a method such as a method in which compressed air is sent from the inside of a mold to expand and stretch a glove-shaped thin film.

The glove of the present invention can be easily contracted by contact with moisture. After shrinking, the degree of shrinkage is usually at least 10%, preferably 20% or more on a length basis in the temperature range of 0 to 35 ° C. under the above-mentioned humidity conditions in order to fit into an unspecified number of human hands. is there.
Therefore, the glove of the present invention does not need to be heated or immersed in warm water, so there is no risk of burns and the glove can be easily used anywhere as long as there is moisture.

The gloves of the present invention can be used under low moisture conditions.
It does not shrink in the temperature range of 100 ° C. Therefore, if moisture is blocked by moisture-proof packaging or the like, storage can be performed stably without shrinking even in places where the temperature may exceed 40 ° C. (in a warehouse in summer, a truck bed during transportation, etc.). This property is not present in the prior art, and is one of the features of the present invention.

The glove of the present invention is usually composed of a stretched product of the resin (A) alone, but may be composed of another material such as a plastic film if necessary. For example, (a) those obtained by laminating the stretched film and another plastic film to form a multilayer structure by co-extrusion molding, heat sealing, bonding, and the like, and (b) laminating the stretched film on a nonwoven fabric, paper, or the like. No.

When the glove of the present invention is actually used, as a method of shrinking, for example, a method of wearing the glove of the present invention and then wetting it with tap water, a method of wearing the glove of the present invention pre-wetted, After wearing the gloves of the present invention, a method of giving moisture by spraying or the like may be used. Of these, the methods of and are preferred.

The glove of the present invention contracts upon contact with moisture in the above-described manner and adheres to the user's hand, and thereafter stretches moderately, so that it can be smoothly expanded and contracted according to the movement of the user. Is possible. Also, attachment and detachment is easy.

The glove of the present invention can be made compact because of its simple shape.

The glove of the present invention does not shrink unless it is re-stretched after the shrinkage is completed, so it is usually used for disposable use.

[0024]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. The shrinkage rate in the examples was determined by leaving each sample under various conditions for one minute, and drawing a vertical line (longitudinal direction of the middle finger portion) and a horizontal line (perpendicular to the longitudinal direction of the middle finger portion) drawn on the back of the glove. It calculated from the ratio of the length before each moisture absorption and after the moisture absorption.

Example 1 A commercially available ethylene vinyl alcohol copolymer (ethylene copolymerization ratio: 32 mol%, manufactured by Kuraray Co., Ltd .; trade name "EVAL EPF-101", melting temperature: 183 ° C.) was dissolved in dimethyl sulfoxide. After that, the solution was denatured by reacting with acetic anhydride, and the solution was added to acetone to precipitate, washed with water and dried, and had a melting temperature of 151 ° C. and a heat of fusion of 16.5 kJ / kg.
And a resin composition whose glass transition temperature is lowered by 30 ° C. or more by water absorption is obtained. Then, the dried and pulverized product of the copolymer was dissolved again in dimethyl sulfoxide, and then formed into a film by a casting method. Then, the film was stretched three times in the MD and TD directions, and heat-treated at 130 ° C. in that state. A film-shaped resin molded product having a thickness of 40 μm and a length and width of 50 cm × 50 cm was obtained. Then, two films were laminated and welded and cut into a handprint to obtain a glove of the present invention. This glove could be easily worn on the hand, shrunk quickly by immersion in water at a water temperature of 35 ° C., and could be fitted exactly on the hand of the wearer. At this time, the shrinkage of the glove was 20% in the vertical direction and 15% in the horizontal direction. In addition, various fine operations could be performed while wearing the gloves. Furthermore, desorption was easy. Further, the glove was placed in a dryer adjusted to a temperature of 50 ° C. and a relative humidity of 20% RH or less and left for 7 days. The dimensional change was less than 1%, and there was no particular problem.

Example 2 The procedure was carried out except that a commercially available ethylene vinyl alcohol copolymer (ethylene copolymerization ratio 47 mol%, manufactured by Kuraray Co., Ltd .; trade name "Eval EPG-110", melting temperature 161 ° C.) was used. As in Example 1, melting temperature 128 ° C., heat of fusion 2
0 kJ / kg and glass transition temperature is 1 due to water absorption
A resin composition having a temperature drop of 5 ° C. or more was obtained. This resin composition is subjected to inflation molding to form a film-shaped moisture-shrinkable resin molded article of the present invention [2] having a thickness of 40 μm (stretch ratio: MD).
Direction 30 times, TD direction 3 times). Using this film, a glove of the present invention was obtained in the same manner as in Example 1. This glove was contracted by being worn on the hand and immersed in water at a water temperature of 25 ° C., and could be easily fitted to the hand of the wearer. In addition, the shrinkage rate of the glove at this time is 22% in the vertical direction,
It was 20% in the horizontal direction. In addition, various fine operations could be performed while wearing the gloves. Furthermore, desorption was easy. Further, the glove was placed in a dryer adjusted to a temperature of 50 ° C. and a relative humidity of 20% RH or less and left for 7 days. The dimensional change was less than 1%, and there was no particular problem.

[0027]

The glove of the present invention has the following effects. (1) Since the glove of the present invention does not require a heating operation or immersion in warm water for shrinkage, there is no need to worry about burns and the like, and it can be easily used anywhere as long as there is moisture. (2) The glove of the present invention shrinks even in places where the temperature may exceed 50 ° C. (in a warehouse in summer, a truck bed during transportation, etc.) if moisture is blocked by moisture-proof packaging or the like. It can be stored stably. (3) Shrinks quickly in response to moisture or moisture and fits snugly into the hand of the wearer, so that the wearer can easily perform fine work. (4) Even after being contracted and brought into close contact with the user's hand, it has an appropriate softness, can be smoothly expanded and contracted, and can be easily attached and detached. (5) Since the glove of the present invention fits to the hand by contracting after wearing, the glove of the present invention may have a simple hand shape at the time of manufacture, and the manufacturing process can be simplified. (6) Further, since the shape is simple, the size can be reduced, and the distribution cost can be reduced. (7) It is easier to put on and take off than conventional rubber gloves that are in close contact with the hand. From the above effects, the glove of the present invention is particularly suitable for disposable use.

Claims (5)

(57) [Claims] 1. A stretch molded product of a resin (A) adjusted to have the following properties (1) and (2),
A glove characterized in that it shrinks by 10% or more on a length basis due to moisture at a temperature of ~ 35 ° C. (1) The glass transition temperature is lowered by absorbing moisture. (2) a melting temperature of 80 ° C. or higher and a heat of fusion of 1 to 80 k;
J / kg. 2. The glove according to claim 1, wherein (A) is a resin that can be melted at a temperature of 250 ° C. or lower. 3. The glove according to claim 1, wherein (A) comprises a copolymer of an olefin and a polymerizable monomer having a hydrophilic group and / or a modified product thereof. 4. The glove according to claim 1, wherein the stretch molded product has a shape of a film, a sheet, and / or a tube. 5. The glove according to claim 4, wherein the stretch-formed product is an inflation film having a stretch ratio of 2 to 50 in both the MD and TD directions.