JPH0657242B2 - Skin protector - Google Patents

Description

Detailed Description of the Invention A. TECHNICAL FIELD OF THE INVENTION The present invention relates to an extremely suitable skin protective material used for protecting the skin from dermatitis due to an epoxy resin composition. Specifically, a thin film of saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH) having excellent resistance to permeation of organic chemicals is used as an intermediate layer, and a linear low-density polyethylene layer is formed on both sides of the intermediate layer. It was characterized by a laminate having a surface layer and each layer being arranged via an adhesive resin, which was previously considered to be "epoxy dermatitis" caused by handling an epoxy resin. However, in reality, it provides a skin protective material that can effectively protect from "dermatitis due to an epoxy resin composition" in which an aliphatic polyamine for curing an epoxy resin acts as the most active component. To do.

B. It is well known from the prior art that an epoxy resin and its curing agent have a property of causing an allergic constitution by causing irritation, and therefore a protective technique for protecting an operator using the same is necessary, Among them, a typical protection technique is a no-touch technique, and protective clothing, gloves, aprons, sleeves, safety glasses, protective equipment such as gas masks, and protective cream are used. In particular, most contact with the epoxy resin and its curing agent (hereinafter referred to as the epoxy resin composition),
Moreover, it is said that rubber, polyvinyl chloride, polyethylene and the like are suitable materials for the protection means in which the protector and the skin are in close contact, and gloves made of the material are used for the protection. . However, regarding the use of protective gloves made of the material, since the “epoxy resin composition dermatitis” active substance of the material, such as the aliphatic poiamine, has high permeability, its allowable use time is short and relatively long. In addition to the drawback of having to replace the protective gloves every short time during the handling of time, sometimes a standard permissible operating time is set depending on the worker's constitution. In this case, since the dermatitis may occur, the allowable use time for eliminating the occurrence of the dermatitis is extremely short, which is uneconomical, inefficient and unsatisfactory. In addition, although the use of a cream for protecting the dermatitis has been attempted, the protective film formed by the cream is extremely thin and is fragile, so a safe protective effect cannot be expected, and it is more difficult than a glove. The effect is much smaller, and even when used in combination with protective gloves, the protective film is thin and fragile as described above, and therefore the protective film is destroyed by friction with the glove. The effect cannot be noticeable. In view of the above circumstances, the "epoxy resin composition dermatitis" has a very low permeability of an active substance, and a skin protective material capable of preventing the occurrence of the dermatitis. In particular, the appearance of the protective gloves is strongly desired. Is the reality. The other
EVOE has excellent organic solvent resistance and organic solvent permeation resistance, but it has not been known at all whether or not EVOE has excellent permeation resistance to dermatitis active substances. In addition, EVOH has a low mechanical strength in general, and cannot withstand the particularly severe bending fatigue required for the protective gloves. Also, EVOH does not have a good heat-sealing property. Therefore, when it is used as one material constituting the glove, it is used by being laminated between a base material layer having excellent mechanical strength and a heat-sealable material. Conventional EVOH is used as an intermediate layer and both surface layers are used. When a thermoplastic resin laminate having a
Pinholes are formed in the laminate, and the ability to block the organic solvents, chemicals, etc. cannot be maintained.

C. The purpose, constitution and effect of the present invention The present inventors have a major drawback that the EVOH film is significantly inferior in flexural fatigue resistance as compared with films of thermoplastic resins such as polyethylene, polypropylene, nylon and thermoplastic polyester. Not only unexpectedly, it seems to be related to the physical properties such as the rigidity of EVOH unexpectedly in the multilayer flexible laminate using the resin layer resistant to bending fatigue and using the EVOH resin layer as the intermediate layer. However, the bending fatigue resistance of the laminate is significantly lower than the bending fatigue resistance of the thermoplastic resin that is strong against bending fatigue, and pinholes are formed in the laminated material with less bending fatigue. That is, the new fact that EVOH film is extremely excellent in the "epoxy resin composition dermatitis" active substance blocking property, and more surprisingly in the occurrence of the pinhole. Until that,
It was found that even if the EVOH layer exceeds flex fatigue that it can withstand by itself, cracks due to flex fatigue, pinholes, etc. do not occur in the EVOH layer, but no decrease in the barrier property is observed. From these viewpoints, a skin protective material having an EVOH layer as an intermediate layer, which is excellent in bending fatigue and can be suitably used for protection of the dermatitis, and in particular, the present invention is completed by intensively studying protective gloves. Was reached.

That is, the present invention has a thin film of a saponified product of an ethylene-vinyl acetate copolymer as an intermediate layer, and has a surface layer composed of a linear low-density polyethylene layer on both sides of the intermediate layer, and each layer has an adhesive resin interposed therebetween. The present invention provides a skin protective material, which is characterized by comprising a laminated body formed by arranging the same.

The flex fatigue resistance is judged by an evaluation test performed using a so-called gel boflex tester. That is, the bending fatigue resistance of various materials, or laminates composed of various materials, can be determined from the data such as the bending frequency dependence under the blocking resistance in the evaluation test and the bending frequency until the pinhole is generated. You can judge. The inventors of the present invention use a gel boflex tester for a single film of various plastic resins and a laminated film having a multi-layered structure made of various resins. With respect to the laminate having a multi-layered structure, several facts were found as a result of measuring the relationship between the number of times of bending and the barrier property in the process up to the occurrence of pinholes. That is, (1) EVOH resin film is extremely poor in bending fatigue resistance,
It cannot be the material that constitutes gloves that can be used practically,
(2) Compared to the EVOH resin film, the film of each resin such as high-pressure method low-density polyethylene, low-pressure method high-density polyethylene, nylon, polypropylene, and thermoplastic polyester that have been commonly used conventionally has a flex fatigue resistance. Although it is remarkably excellent, the flexural fatigue resistance of the laminate film in which the resin film is laminated with EVOH as an intermediate layer is not clear in detail, but a significant decrease that is considered to be due to the presence of the EVOH layer, that is, the resin A remarkable decrease is seen in comparison with the excellent flex fatigue resistance of the single film, (3) more surprisingly, until the occurrence of pinholes in the laminate having the EVOH layer as the intermediate layer, Almost no decrease in dermatitis active substance blocking property, (4) Above all, it was recognized that the laminate using a linear low-density polyethylene layer on both surface layers significantly improved flexion fatigue. Was .

The improvement in flexural fatigue resistance is remarkable only in the case where the linear low-density polyethylene is used in any of the surface layers, in the laminate having the structure in which EVOH is the intermediate layer. Although details of the phenomenon have not been clarified yet, the effect of the improvement is that the carbon number of α-olefin, which is a copolymerization component of the linear low-density polyethylene, the heat of fusion by the thermal analysis of a differential scanning calorimeter and the Young's They are deeply and deeply involved and are particularly noticeable when linear low density polyethylenes are employed, which are in the particular areas selected.

D More Detailed Description of the Invention The linear low-density polyethylene used in the present invention is a linear low-density polyethylene having substantially no long-chain branch. Generally, a quantitative measure of the number of long chain branches G = [η] _b
/ [Η] _l ([η] _b is the intrinsic viscosity of branched polyethylene,
[Η] _l has an intrinsic viscosity of linear polyethylene having the same molecular weight as that of branched polyethylene of almost 1 (generally 0.9 to 0.9).
It is in the range of 1 and often close to 1), and the density is 0.
910 to 0.945. (The G value of the conventional ordinary high-pressure low-density polyethylene is 0.1 to 0.6.) The method for producing linear low-density polyethylene is not particularly limited. The pressure is 7 to 45 kg / cm ² (typically 2000 to 3000 kg for high-pressure low density polyethylene).
/ cm ² ) at a temperature of 75 to 100 ° C. (120 to 250 ° C. in the case of high-pressure low density polyethylene), using a chromium-based catalyst or a Ziegler catalyst, the number of carbon atoms is 3 or more, preferably 4 or more, more preferably 5 There is a method in which ethylene is copolymerized with α-olefin of 10 to 10, for example, α-olefin such as propylene, butene-1, methylbenten-1, hexene-1, octene-1 as a copolymerization component. As the polymerization method, a solution method liquid phase method, a slurry method liquid phase method, a fluidized bed gas phase method, a general bed gas phase method or the like is used.

As described above, the effects of the present invention, the carbon number of the α-olefin, the heat of fusion of the linear low-density polyethylene by the thermal analysis of the differential scanning calorimeter, and the Young's modulus are deeply concerned. , More specifically, as follows. Linear low density polyethylene is preferably used in the present invention, but the heat of solution is 25 cal / g or less, preferably 25 to
5cal / g or Young's modulus at 20 ℃ is 2
2 kg / mm ² or less, preferably 22~3kg / mm ^2, more preferably more pronounced the effect of the present invention for the polyethylene is 22~5kg / mm ^2, most noticeable particularly when they are in the region Is. Those having the heat of fusion and Young's modulus in the above-mentioned ranges are somewhat different depending on the polymerization method and the polymerization conditions, but generally speaking, the content of the α-olefin as a copolymerization component is about 2 mol% or more, preferably about It is often obtained in the range of 2 to 7 mol%. For linear low-density polyethylene in which the copolymerization component is butene-1, the heat of fusion is 1
The effect of the present invention is more remarkable when the Young's modulus at 5 cal / g or less or at 20 ° C. is 12 kg / mm ² or less, and particularly when both are in the above range, the effect is most remarkable. You can enjoy it. The low-density polyethylene having the heat of fusion and Young's modulus in the above-mentioned range is generally obtained in a range where the butene-1 content is about 4 mol% or more. If the content is too high, the other physical properties of the polyethylene become unsatisfactory, which is not preferable, and the content is at most several mol%, for example, 7 mol%.
Is desirable. Further, the effect of the present invention can be enjoyed for the linear low-density polyethylene having the heat of fusion and / or Young's modulus in the above-mentioned specific region as described above, but particularly α-olefin having 5 or more carbon atoms, for example, 5 to 10 carbon atoms. The effect can be remarkably enjoyed with respect to the polyethylene containing as a copolymerization component. In this case, for the same reason as above, the content of the α-olefin is 2 to 7 mol%,
More specifically, 2 to 6 mol% is preferable, and the heat of fusion is related to the content of α-olefin as described above, but the heat of fusion is 25 to 5 cal / g. Also, Young's modulus is 22 kg / mm ² or less, preferably 22 to
3 kg / mm ^2, more preferably from 22~5kg / mm ^2. Among the olefins, the effect of the present invention is more remarkable, and linear low-density polyethylene containing 4-methyl-1-pentene as a copolymerization component, which is easily obtained industrially, is one of the most preferable ones. . In the case of conventional high-pressure method low-density polyethylene, the heat of fusion by the thermal analysis of the differential scanning calorimeter or /
And even if the Young's modulus is in the above range, the effect of the present invention cannot be enjoyed.

Despite the extremely poor pinhole resistance of the EVOH single film, the linear low density polyethylene of the present invention is used for any surface layer, and the pinhole resistance of the laminated film having the EVOH layer as an intermediate layer At the time when the
That is, judging from the characteristics of the EVOH single film, it is natural that cracks or pinholes are generated in the intermediate layer and the barrier property of the laminate is expected to deteriorate. The point that no decrease is observed is extremely specific.

Regarding the solution viscosity of the linear low-density polyethylene, particularly when the laminate is obtained by the coextrusion method, one having a relatively similar melt viscosity is selected from the viewpoint of the melt viscosity matching with EVOH resin and the like. It is more preferable to use.

In the case of the laminate of the present invention, if the surface layer made of the linear low-density polyethylene is too thin, for example, 5 μm
Since the other physical properties will be deteriorated if it becomes the following, the thickness is preferably 5 μm or more, and more preferably 10 μm or more. Further, if the thickness is increased too much, the functionality of the glove is deteriorated, so that each layer of the surface layer is usually used in an amount of 40 μm or less, preferably 30 μm or less.

The EVOH resin used in the present invention has an ethylene content of 25 to 6
Those having 0 mol% and a saponification degree of 95% or more are preferably used. When the ethylene content is 25 mol% or less, not only the moldability is lowered but also the rigidity of the EVOH is considered to be related, but the effect of the present invention is diminished, and the ethylene content is 60 mol%. If it exceeds, the rigidity is reduced, but the barrier property of the dermatitis active substance, which is the most characteristic of the resin, is lowered and the resin becomes unsatisfactory. The EVOH resin is 25-60
Even if a blend of two or more resins having different ethylene contents having an ethylene content within the range of mol% is within the range showing compatibility, the effects of the present invention are enjoyed. You can The saponification degree of the resin is preferably 95% or more, and less than 95% is not preferable because the blocking property of the active substance is lowered. Furthermore, EVOH treated with a boron compound such as boric acid, a third component such as a silicon-containing olefinic unsaturated monomer is copolymerized with ethylene and vinyl acetate, and modified EVOH obtained by saponification is also melt-moldable. The effects of the present invention can be enjoyed as long as the degree of modification is within a range that does not impair the barrier property.

As mentioned above, in the case of the EVOH single layer, the bending fatigue resistance is extremely poor and shows a slight improvement tendency as the thickness decreases, but this is far higher than the practically required bending fatigue resistance. It's just a phenomenon in a field that is beyond reach. However, in the constitution of the laminated packaging material of the present invention, the layer thickness dependency of EVOH, which depends on the intermediate layer, to the number of times of bending of the Gelboflex tester leading to pinholes due to bending fatigue is extremely remarkably expressed. Specificity is recognized. The EV
If the thickness of the OH layer exceeds 20μ, the bending fatigue resistance decreases,
This is not preferable because the effects of the present invention are diminished. In order to fully enjoy the effects of the present invention, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 15 μm or less. From the viewpoint of bending fatigue resistance, 10 μm or less is most preferable.
More preferably, the thickness is selected to be 10 μm or less, and two or more EVOH layers are provided in accordance with the degree of high demand for the buyer property. From the viewpoint of resistance to bending fatigue, it is preferable that the thickness of the EVOH layer is as small as possible, but the difficulty in terms of molding technology increases accordingly. Practically, 2 μm or more is preferable, and 5 μm or more is more preferable from the viewpoint of being relatively difficult. When the thickness is 2 μm or less, pinholes are often generated in the EVOH layer when the laminate is obtained, and the barrier property may be unsatisfactory, which is not preferable.

The skin protective material of the present invention is required to be one in which each layer is arranged via an adhesive resin layer, and it causes delamination at the time of flex fatigue resistance test by the Gelbo Flex Tester. must not. When the delamination is caused, the effect of improving the bending fatigue resistance of the EVOH layer located in the intermediate layer due to the lamination is not recognized, and the phenomenon that the active substance blocking property is deteriorated due to the damage of the EVOH layer is caused by the lamination. The effect of the present invention cannot be enjoyed because the pinholes are already recognized at the stage when the film is not recognized.
The adhesive resin used in the present invention is a linear low-density polyethylene layer, and also has adhesiveness with an EVOH layer, and a carboxyl group-containing modified product of polyethylene, a carboxyl group-containing modified product of an ethylene-vinyl acetate copolymer, and A carboxyl group-containing modified product of an ethylene-acrylic acid ester copolymer is preferred. It is particularly preferred that the carboxyl group-containing modified product is a maleic anhydride modified product. Among them, the following are more preferable as the adhesive resin. One of them is a modified LLDPE obtained by chemically binding maleic anhydride to 0.01 to 15% by weight, more preferably 0.05 to 10% by weight of the specific LLDPE preferably used as a surface layer according to the present invention, or Modified LLDPE and unmodified LLDP
The blend of E, wherein the content of chemically bound maleic anhydride contained in the blend is 0.01 to 10% by weight, more preferably 0.05 to 10% by weight. The other is an adhesive resin of a specific ethylene-vinyl acetate copolymer type, which includes the following. That is, (1) ethylene having a vinyl acetate content of 35 to 55% by weight
Modified malein-vinyl acetate copolymer obtained by chemically bonding maleic anhydride to vinyl acetate copolymer in an amount of 0.01 to 15% by weight, and (2) ethylene-vinyl acetate copolymer containing maleic anhydride in an amount of 0.01 to 15% by weight. 15% by weight chemically bound,
Consisting of the resulting modified ethylene-vinyl acetate copolymer,
Moreover, (A) at least one modified copolymer having a vinyl acetate content of 20 to 45% by weight, and (B) the content of 35 to 55% by weight.
A blend of at least one of the modified copolymers of
The difference between the vinyl acetate content of (A) and the content of (B) adjacent to each other is at least 10% by weight, and the blending ratio (weight) A: B is 60:40 to 5:95. Modified copolymer resin composition, (3) (C) ethylene-vinyl acetate copolymer having a vinyl acetate content of 20 to 55% by weight and maleic anhydride
At least one modified ethylene-vinyl acetate copolymer obtained by chemically bonding (X) up to 15% by weight and (D) at least one ethylene-acetic acid having a vinyl acetate content of 20 to 55% by weight. It comprises a blend with a vinyl copolymer, and the blend has a vinyl acetate content of 35% by weight or more.
A resin composition containing 40% by weight or more of (C) and / or (D) and containing 0.01% by weight or more of chemically bonded X is more preferably used. Still another is an adhesive resin of a specific ethylene-acrylic acid ester copolymer system, which includes the following. That is, (E) an ethylene-acrylic acid ester copolymer having an acrylic acid ester content of 20 to 35% by weight, maleic anhydride (X),
At least one modified ethylene-acrylic acid ester copolymer obtained by chemically bonding so as to have a carboxyl group content of 0.03 to 2 meq / g and (F) acrylic acid ester content of 20 to 35% by weight % Of at least one ethylene-acrylic acid ester copolymer, and satisfying the following formulas (I) and (II). Most preferably, the acrylic acid ester is acrylic acid ethyl ester.

However, i; integer of 1 to n j; integer of 1 to m n, m; positive integer C _Ei ; content of carboxyl group by chemically bonded X component contained in copolymerization ( _Ei ) (meq / g) _Ei ; Copolymer ( _Ei ) blend ratio (weight fraction) _Fj ; Copolymer ( _Fj ) blend ratio (weight fraction) The laminate according to the present invention can be obtained by a method known per se.
The present invention is not limited to the lamination method, although it is more preferably obtained by the coextrusion method. The protective glove of the present invention comprises the LLDP having a heat-sealable surface layer of the laminate.
Since it is E 2, it can be obtained, for example, by stacking two sheets of the laminate and heat-sealing the gloves, or by cutting the gloves simultaneously with the heat-sealing.

In the present invention, EVOH is used as an intermediate layer on both sides of this layer.
It is free to provide another resin layer on the laminated material provided with the LLDPE layer as long as the object of the present invention is not impaired.

The skin protective material according to the present invention can be suitably used not only as protective gloves which are required to have flexural fatigue resistance, but also as a material for protective clothing, aprons, sleeves and the like for protection against the dermatitis. The protective means, protective clothing, etc. using the protective material as a constituent material can be used in a usage mode in which the protective material itself comes into contact with the skin, and can also be used by overlapping with gloved clothing etc. composed of other materials. it can. It is appropriate to use the skin protective material according to the present invention by superposing it on a means, clothes or the like made of a conventional material as a constituent material in view of physical damage during work and securing of hygroscopicity.

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Example 1 An intermediate layer of EVOH resin having an ethylen content of 30 mol% and a saponification degree of 99.4% and having a thickness of 12 μ, and 4-methyl-1-pentene having a thickness of 15 μ on each side of the intermediate layer as a copolymerization component. , Melt index (hereinafter referred to as MI value) measured according to ASTM D-1238-65T under the conditions of 190 ° C. and 2160 g load, containing 3.2 mol% of the copolymerization component 2.1 Heat of fusion by differential scanning calorimeter Has a surface layer consisting of linear low-density polyethylene (hereinafter referred to as LLDPE) of 19 cal / g, with a thickness of 5μ between each layer of vinyl acetate content of 40% by weight and maleic anhydride modification degree of 1.5% by weight. A laminated film arranged via an adhesive resin layer made of an ethylene-vinyl acetate copolymer was obtained by a coextrusion method using three extruders and a three-layer, five-layer multi-layer die head. A bending fatigue test was performed on the obtained laminated film until generation of pinholes was observed in the laminated film.

For the bending fatigue test, a gel inflex tester (manufactured by Rigaku Kogyo Co., Ltd.) was used, and a 12 in x 8 in sample piece was measured. No cylindrical shape, gripping both ends, initial gripping interval 7 in,
Gripping interval of maximum bending ratio 1 in, first of stroke Then, add a twist of 440 °, and then Is a reciprocating motion of linear horizontal motion at a speed of 40 times / min at a temperature of 20 ° C. and a relative temperature of 65%. No pinhole was observed until the bending fatigue test was repeated 5000 times. Moreover, no delamination between the layers was observed. The LLDPE film was separately obtained, and the Young's modulus was adjusted to 20 kg at a result of 13 kg / mm ² .

When the protective gloves were obtained from the laminated film and used to handle an epoxy resin containing diethylenetriamine as a curing agent for 20 people, none of them developed the dermatitis. The working time was 8 hours in total. Further, the gloves were obtained from the laminate after 3000 reciprocating flexion fatigue tests, and the same procedure as above was carried out, but none of them caused the dermatitis. Total work time 6
It was time.

In the above work, so-called work gloves were used as the outermost layer of the thin rubber gloves on the innermost side, and the protective gloves of the present invention were protected from the occurrence of defective portions due to external factors such as scratching.

Example 2 The procedure of Example 1 was repeated except that an EVOH resin having an ethylene content of 45 mol% and a saponification degree of 99.2% was used as the intermediate layer. No pinhole was observed until 5500 reciprocation of the bending fatigue test, and one pinhole was confirmed after 5600 reciprocation.

The same procedure as in Example 1 was carried out except that the protective gloves were obtained from the laminated film, and the protective gloves were used to handle the epoxy resin having triethylenetriamine as the curing agent. No one had dermatitis.

Example 3 A laminated film having a structure of D / Ad / E / Ad / F / Ad / G was obtained by using a coextrusion equipment having a multilayer die head for 3 types of 7 layers. Each layer is made of the following resin and layer thickness.

Ad: Modified ethylene-vinyl acetate copolymer 4 having a vinyl acetate content of 25% by weight and a maleic anhydride modification degree of 1.0% by weight
Copolymerization of a blend of 0 parts by weight and 60 parts by weight of an ethylene-vinyl acetate copolymer of 40% by weight of vinyl acetate and an adhesive resin layer D, G having a thickness of 5 μm: 4.1% by weight of 4-methyl-1-pentene. Melt index contained as a component 2.3 LLDPE layers E and F having a thickness of 15μ with a heat of fusion of 15 cal / g by a differential scanning calorimeter: 38 mol% ethylene content, 99.4% saponification degree, and an EVOH resin layer having a thickness of 6μ A bending fatigue test was performed according to Example 1. The flex fatigue was tested. No pinholes were found even after 6000 reciprocations. No delamination between the layers was observed.
The Young's modulus of the LLDPE film separately obtained and measured at 20 ° C. was 7.5 kg / mm ² .

The protective gloves were obtained from the laminated film, and the test was conducted in the same manner as in Example 1 except that the protective gloves were used to confirm the effect of preventing the occurrence of the dermatitis. As in Example 1, none of the individuals developed the dermatitis.

Example 4 In Example 2, as the adhesive resin, 42 parts by weight of a modified ethylene-vinyl acetate copolymer having a vinyl acetate content of 26% by weight and a maleic anhydride modification degree of 0.75% by weight, and a vinyl acetate content of 45% by weight maleic anhydride were used. Example 2 was carried out in the same manner as in Example 2 except that a blended resin consisting of 58 parts by weight of a modified ethylene-vinyl acetate copolymer having a modification degree of 1.1% by weight was used. No pinholes were observed even after 5500 reciprocating flexion fatigue tests, and no one suffered from the dermatitis during the epoxy resin handling work.

Example 5 In Example 1, except that the same LLDPE as that used for the surface layer was modified with a maleic anhydride modification degree (chemical bonding amount of maleic anhydride to LLDPE: 0.7% by weight) of LLDPE as an adhesive resin, The same procedure as in Example 1 was performed. No pinhole was observed even after 5000 cycles of the bending fatigue test, and none of the dermatitis patients was observed during the epoxy resin handling work.

Example 6 A copolymer having 1-heptene as a copolymerization component in both surface layers in Example 1 and having a content of 2.9 mol% and a heat of fusion of 21 cal / g by a differential scanning calorimeter was separately obtained and measured at 20 ° C. The same procedure as in Example 1 was carried out except that LLDPE having a Young's modulus of 15 kg / mm ² was used and the ethylene-ethyl acrylate resin obtained as described below was used as the adhesive resin.

The adhesive resin was obtained as follows. That is, the content of the ethyl acrylate component is 25% by weight, and the MI (190 ° C, 216
100 parts by weight of an ethylene-ethyl acrylate copolymer having a load of 0 g) of 6 g / 10 min and 20 parts by weight of maleic anhydride were dissolved in 1000 parts by weight of purified xylene and kept at 140 ° C.
A solution prepared by dissolving 0.8 parts by weight of benzoyl peroxide in 100 parts by weight of xylene was added dropwise to this solution with stirring at 140 ° C. over 3 hours, and then stirring was continued for 20 minutes. After cooling, the reaction solution was poured into a large amount of purified acetone to precipitate a polymer. The polymer obtained was purified by reprecipitation using purified xylene as a solvent and purified acetone as a non-solvent.
The obtained polymer contained 24.5% by weight of ethyl acrylate component and 0.57 meq / g of carboxyl groups. MI is 3.
It was 2 g / 10 minutes. A / B = 53/4 of the polymer (A) and an ethylene-ethyl acrylate copolymer (B) containing 25% by weight of an ethyl acrylate component and having an MI of 6 g / 10 min.
7 (weight ratio) was compounded and used as an adhesive resin.

No pinholes were found even after 5000 cycles of the bending fatigue test, and no one had developed the dermatitis during the epoxy resin handling work.

Example 7 In Example 1, butene-1 was used as a copolymerization component, the content of the component was 5.1 mol%, and the heat of fusion by a differential scanning calorimeter was 12
The same procedure as in Example 1 was performed except that a cal / g film was separately obtained and both surface layers were composed of LLDPE having Young's modulus of 8 kg / mm ² measured at 20 ° C.

No pinhole was observed even after 5000 cycles of the bending fatigue test, and no one had developed the dermatitis during the work of handling the epoxy resin.

Claims (12)

[Claims] 1. A thin film of a saponified product of an ethylene-vinyl acetate copolymer is used as an intermediate layer, and a surface layer composed of a linear low-density polyethylene layer is provided on both sides of the intermediate layer, and each layer has an adhesive resin layer. A skin protective material, which is composed of a laminated body that is disposed through. 2. The skin protective material according to claim 1, wherein the linear low-density polyethylene has α-olefin having a carbon number of 4 or more as a copolymerization component. 3. The skin protective material according to claim 1, which has a heat of fusion of 25 cal / g or less based on a thermal analysis of a linear low density polyethylene differential scanning calorimeter. 4. The skin protection according to claim 1, wherein the linear low-density polyethylene has butene-1 as a copolymerization component and the heat of fusion by thermal analysis of a differential scanning calorimeter is 15 cal / g or less. Material. 5. A linear low density polyethylene having a Young's modulus at 20 ° C. of 22 kg / mm ² or less.
Item 5. The skin protective material according to any one of items 3 to 3. 6. A linear low-density polyethylene having butene-1 as a copolymerization component, and a Young's modulus at 20 ° C. of 12 kg / mm ²
The skin protective material according to claim 1 or 4, which is as follows. 7. The skin protective material according to claim 1, 3, or 5, wherein the linear low-density polyethylene has α-olefin having a carbon number of 5 or more as a copolymerization component. 8. The linear low-density polyethylene is 4-methyl-
The skin protective material according to claim 1, which comprises 1-pentene as a copolymerization component. 9. The skin protection according to any one of claims 1 to 8, wherein the saponified ethylene-vinyl acetate copolymer has an ethylene content of 25 to 60 mol% and a saponification degree of 95% or more. Material. 10. The skin protective material according to claim 1, wherein the intermediate layer has a thickness of 20 μm or less. 11. The skin protective material according to any one of claims 1 to 10, wherein the intermediate layer made of a saponified product of an ethylene-vinyl acetate copolymer has at least two layers. 12. An intermediate layer comprising a saponified product of an ethylene-vinyl acetate copolymer, wherein each intermediate layer comprises at least two layers each having a thickness of 10 μm or less.
The skin protective material according to any one of the above.