JP3161835B2 - Thermal adhesive laminate and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

[0001] The present invention relates to a heat-adhesive laminate and a method for producing the same, and more particularly, it can be used for interlining such as collars and cuffs, chair surface materials, waterproof sheets, heat-adhesive labels (for clothing), and other covers. The present invention relates to a heat-adhesive laminate having excellent adhesive strength between fabrics and excellent water-washing resistance and dry-cleaning resistance, and a method for efficiently producing the heat-adhesive laminate.

[0002]

2. Description of the Related Art Conventionally, ethylene-vinyl acetate copolymer (EVA) has been the mainstay of hot-melt adhesives which have been used for clothing (for example, interlining), but the adhesive strength is low. And its dry cleaning resistance was very poor, so its use range was naturally limited. In order to improve this, for example, EVA is completely saponified or partially saponified, or the saponified EVA is graft-polymerized with acrylic acid, maleic acid or the like.
A polymer obtained by modifying EVA by a method of introducing a carboxyl group by reacting a part of the hydroxyl group in the molecule of the saponified product with a dicarboxylic acid or the like is also used. Although the adhesive force is considerably improved by such a modification method in which a polar group is introduced, the solvent resistance (dry cleaning resistance) has not been sufficiently improved yet. Clothes manufactured using such an adhesive have a drawback that, when dry-cleaned, the adhesive swells due to a solvent such as perchlorethylene, and the adhered cloth is partially peeled off.
Polyamide-based adhesives with relatively high adhesive strength are also used, but because of their high water absorption, in addition to being difficult to wash with water, bleeding-out of the resin and the like at the time of adhesive pressing occurs, and sewing products There are drawbacks in that the appearance is poor, the texture of the fabric is impaired because the resin itself is too hard, and the price is extremely high. In addition, polyester-based adhesives are also used, but polyester-based fibers exhibit strong adhesive strength, but adhesive strength to other types of fabrics made of natural fibers or synthetic fibers, washing resistance. Since the adhesive property has not yet been obtained so strong that it can withstand practical use, the range of use of this adhesive is also limited.

[0003]

At present, it has strong adhesiveness to a wide variety of fabrics, and is excellent in water-washing resistance and dry-cleaning resistance. Inexpensive resin-adhesive cloths, heat-adhesive laminates used for waterproof sheets and other covers and the like and methods for producing the same have not yet been established. The present invention provides a thermo-adhesive laminate which solves these problems and a method for producing the thermo-adhesive laminate.

[0004]

Means for Solving the Invention Accordingly, the present inventors have
In view of the above situation, intensive studies have been made to develop a heat-adhesive laminate which has solved the drawbacks of the conventional method. As a result, by using a specific polyolefin-based resin composition as an adhesive, a heat-adhesive laminate having strong adhesion to a wide variety of fabrics and having water-washing resistance and dry-cleaning resistance can be obtained. I found what I could get. The present invention has been completed based on such findings.
That is, the present invention provides (A) a multi-component copolymer comprising ethylene, a radical-polymerizable acid anhydride and another radical-polymerizable comonomer, wherein the radical-polymerizable acid anhydride in the ethylene-based multi-component copolymer is The ratio of units derived from is 0.
1 to 5% by weight, 10 to 90% by weight of an ethylene-based multi-component copolymer having a ratio of units derived from other radically polymerizable comonomers of 3 to 50% by weight, and (B) 10 to 90% by weight of a polyolefin-based resin And (C) laminating and fusing a resin composition comprising 1 to 40% by weight of a saponified ethylene-vinyl acetate copolymer on a fabric, and the thermoadhesive laminate. Is provided.

[0005] The resin composition used for producing the heat-adhesive laminate of the present invention comprises the above-mentioned (A) an ethylene-based multi-component copolymer, (B) a polyolefin-based resin and (C) an ethylene-vinyl acetate copolymer. It is mainly composed of a saponified polymer. First, in the present invention, the ethylene-based multi-component copolymer as the component (A) constituting the resin composition is a multi-component copolymer comprising ethylene, a radical polymerizable acid anhydride and a radical polymerizable monomer. Here, the radically polymerizable acid anhydride has one or more each of a radically polymerizable unsaturated bond and an acid anhydride group in the molecule, and is capable of introducing an acid anhydride group into the molecule by polymerization. Compound. Specific examples of such a compound include, for example, maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic anhydride, and a compound having at most 18 carbon atoms. Alkadienyl succinic anhydride having a double bond at a certain terminal is exemplified. These may be used alone or in combination of two or more. Among these, maleic anhydride and itaconic anhydride are particularly preferred.

The radical polymerizable monomers include:
There are various compounds, for example, ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, (meth) acrylic amide compounds, ethylenically unsaturated acid compounds,
Examples include ethylenically unsaturated ether compounds, ethylenically unsaturated hydrocarbon compounds, and other compounds. Specifically, examples of the ethylenically unsaturated ester compound include vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Examples include hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and benzyl (meth) acrylate. Examples of the ethylenically unsaturated amide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide,
-Propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide; N, N-
Dimethyl (meth) acrylamide; N, N-diethyl (meth) acrylamide and the like. Examples of (meth) acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide;
N, N-dimethyl (meth) acrylamide; N-ethyl (meth) acrylamide; N, N-diethyl (meth) acrylamide. Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid. As the ethylenically unsaturated ether compound,
For example, methyl vinyl ether, ethyl vinyl ether, propyl nyl ether, butyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and the like can be mentioned. Examples of the ethylenically unsaturated hydrocarbon compound and other compounds include styrene, α-mesotylstyrene, acrylonitrile, methacrylonitrile, acrolein, trimethoxyvinylsilane, vinyl chloride, and vinylidene chloride. Among these, (meth) acrylic esters, (meth) acrylic amide, and (meth) acrylic acid are particularly preferred compounds. However, since acrylic acid may react with maleic anhydride depending on conditions, (meth) acrylic amide is most preferable. These comonomers may be used alone or in combination of two or more. The ratio of units derived from the radical polymerizable acid anhydride and the other radical polymerizable comonomer in the ethylene-based multi-component copolymer is 0.1 to 5% by weight, 3 to 50% by weight, and preferably 0 to 5% by weight, respectively. The range is from 0.4 to 4.0% by weight and from 5 to 40% by weight. If the ratio of the radically polymerizable acid anhydride is less than 0.1% by weight, the adhesive performance is insufficient, and good adhesive strength cannot be obtained. On the other hand, when the content exceeds 5% by weight, the effect of improving the adhesive strength is almost negligible and economical. On the other hand, when the proportion of the radical polymerizable comonomer is less than 3% by weight, the crystalline melting point of the ethylene-based multi-component copolymer does not become sufficiently low, and the low-temperature adhesion characteristic of the present invention cannot be exhibited. If the content exceeds 50% by weight, it becomes difficult to handle the resin, and the heat resistance and dry cleaning resistance of the product are reduced.

[0007] In producing the ethylene-based multi-component copolymer of the component (A) according to the present invention, basically, ordinary low-density polyethylene production equipment and its technology can be used. Generally, the bulk polymerization method is used to obtain 700
It is produced by radical polymerization in a temperature range of 100 to 300 ° C. under a pressure of ０００3000 atm. Preferably, the polymerization pressure is from 1000 to 2500 atm and the polymerization temperature is an average temperature in the reactor of from 150 to 270 ° C. When the polymerization pressure is less than 700 atm, the molecular weight of the polymer becomes low, and the resin physical properties of the resin composition deteriorate. When the pressure exceeds 3,000 atm, the production cost is increased, but is practically meaningless. If the average polymerization temperature is lower than 100 ° C., the polymerization reaction is not stable, and the conversion into a copolymer is reduced, which is economically problematic. On the other hand, when the temperature exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, the risk of runaway reaction occurs. And it is preferable to use a vessel type reactor as a polymerization apparatus. In particular, radical polymerizable acid anhydrides have poor polymerization stability, and therefore require a high degree of uniformity in the reactor. If necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization. Further, by dividing the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

[0008] That is, the production of the ethylene-based multi-component copolymer is carried out in the presence of at least one free radical initiator under the above reaction conditions. Here, specific examples of the free radical initiator include, for example, oxygen; dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, acetyl peroxide, i-butylene. Diacyl peroxides such as ruperoxide and octanoyl peroxide;
-Peroxycarbonates such as propyl peroxycarbonate and di-2-ethylhexylperoxycarbonate; peroxyesters such as t-butyl-peroxypivalate and t-butylperoxylaurate; methyl ethyl ketone peroxide; cyclohexanone peroxide Ketone peroxides such as 1,1-bis-t-butylperoxycyclohexane; peroxyketals such as 2,2-bis-t-butylperoxyoctane; t-
Examples thereof include hydroperoxides such as butyl hydroperoxide and cumene hydroperoxide, and azo compounds such as 2,2-azo-i-butyronitrile. In the polymerization, various chain transfer agents can be used as a molecular weight regulator. Specific examples of the chain transfer agent include olefins such as propylene, butene, and hexene; paraffins such as ethane, propane, and butane;
Examples include carbonyl compounds such as acetone, methyl ethyl ketone, and methyl acetate, and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. The ethylene-based multi-component copolymer (A) produced in this manner melts at a relatively low temperature, and is rich in physicochemical interaction and reactivity with various base materials. Even if the resin composition is formed at a low temperature, it plays a large role in exhibiting high adhesive strength.

Next, in the present invention, specific examples of the polyolefin resin as the component (B) constituting the resin composition include high-density polyethylene, low-density polyethylene, polypropylene, potaisoprene, polybutene, and the like.
Copolymers of poly-3-methylbutene-1, poly-4-methylpentene-1, polybutadiene and the constituent units of the above resins, for example, ethylene-propylene copolymer, butene-1,4-methylpentene-1, Examples thereof include linear low-density polyethylene having hexene-1, octene-1 or the like as a comonomer, a block copolymer of propylene-ethylene, or a mixture of these resins. In the present invention, a polyolefin-based resin having a melting point of more than 100 ° C. is preferable in terms of dry cleaning resistance.
Here, the melting point is determined by DSC (Differential Scanning Calor
i.), melting peak temperature measured with instruments such as DTA (Differential Thermal Analysis). Polyolefin-based resins are used for the purpose of maintaining dry cleaning resistance and adhesive strength when used at high temperatures.
If the temperature is lower than 00 ° C., this effect is not sufficient.

In the present invention, the saponified ethylene-vinyl acetate copolymer (EVA saponified) as the component (C) constituting the resin composition is obtained by saponifying a copolymer of ethylene and vinyl acetate. It is obtained. That is, a solution under a high-pressure radical polymerization method at 1000 to 3000 atm or a solution under 100 to 400 atm, or an ethylene content of 55 to 9 produced by a method such as an emulsion polymerization method.
It is obtained by hydrolyzing an ethylene-vinyl acetate copolymer with 9 mol% and a melt index of 0.1 to 500 g / min with an acid or an alkali. The degree of saponification is 5-100 mol%
Is effective, preferably from 10 to 100 mol%, more preferably from 20 to 100 mol%. In the present invention, the saponified EVA has a melting point of 12
It is preferably 0 ° C. or lower. EVA saponified products having a melting point of more than 120 ° C. are not preferred because low-temperature adhesiveness, one of the features of the present invention, is impaired.

In the present invention, the resin composition comprises the above components (A), (B) and (C) as main components. And the mixing ratio of each component is
10 to 90% by weight, preferably 15 to 80% by weight, of the ethylene-based multi-component copolymer (A) and 10 to 90% by weight, preferably 10 to 8% by weight of the polyolefin-based resin (B).
It is a resin composition comprising 0% by weight and 1 to 40% by weight, preferably 5 to 40% by weight of an EVA saponified component (C). Here, if the amount of the EVA saponified component (C) is less than 1% by weight, the effect of improving the adhesive strength cannot be expected. On the other hand, if it exceeds 40% by weight, there is no longer any effect in improving the adhesive strength,
EVA saponified is expensive and not economical.
The resin composition of the present invention as described above is strongly bonded by heat treatment at a relatively low temperature, is excellent in maintaining the adhesive strength at a high temperature, and is excellent in washing resistance and dry cleaning resistance. .

In the present invention, the resin composition comprises the above components (A), (B) and (C) as main components,
It is prepared by mixing each component according to each mixing ratio. In mixing the components, various commonly known methods can be used. Specifically, for example, a method of dissolving and reprecipitating each component in a solvent such as high-temperature toluene, and a method of mixing each component in a molten state, that is, a commonly used pressure kneader, roll, Banbury mixer , A static mixer, a method using a screw type extruder, or the like. In some cases, each component may be dry blended to form a composition at the time of molding. The resin composition may further contain various additives, in addition to the components (A), (B) and (C), as needed, as long as the object of the present invention is not impaired.
Compounding agents, fillers and the like can be compounded. Specifically, for example, inorganic materials such as antioxidants (heat resistance stability), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), and glass fillers Examples include fillers, organic fillers, reinforcing agents, coloring agents (dyes and pigments), foaming agents, and fragrances.

[0013] The heat-adhesive laminate of the present invention is produced by using the above-mentioned resin composition and laminating it on a fabric using various methods. Here, the resin composition is often obtained in a substantially solid state, and according to each application method, after being laminated on a fabric, the fabric is heated and pressed to a temperature equal to or higher than the melting point of the resin composition to impregnate the fabric. The heat-adhesive laminate of the present invention is obtained. For example, when it is used as a powder, it is pulverized by a suitable pulverizing device, for example, a freezing pulverizer or the like, and is used as a powder having an average particle size of 500 μm (35 mesh) or less by a classifier. In this case, for example, when the average particle diameter is larger than 800 μm exceeds 10%, it becomes difficult to uniformly mix these resin powders in fine cloth of the cloth, and a sufficient effect cannot be obtained. When used as a film, the film is formed into a film of 10 to 500 μm by inflation molding, T-die molding or the like, and then laminated on a fabric. Here, if the film thickness is less than 10 μm, the adhesive strength is insufficient, and if it exceeds 500 μm, it may undesirably exude to the surface through the texture. Then, the resin composition can be coated on a cloth, an interlining and the like in a molten state. In this case, the thickness of the melt coat layer is preferably set to 10 to 500 μm.
If the thickness is less than 10 μm, the adhesive strength is insufficient, and if it exceeds 500 μm, it may undesirably exude to the surface through the texture. The resin composition laminated on the fabric in this manner is then impregnated into the fabric with an iron, a press, or the like, to obtain a heat-adhesive laminate that can be used for glued interlining and other uses.

In the present invention, when laminating the resin composition, the fabric is not particularly limited. For example, synthetic fibers such as nylon, polyester, polyurethane, and acrylic, regenerated fibers such as rayon and acetate, inorganic fibers such as glass, natural fibers such as cotton, hemp, silk, and wool, and various fabrics obtained by blending these. Is mentioned. In addition, as the fabric, a known fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric can be arbitrarily selected. As described above, in the case of a powder, the resin composition is sprinkled on these cloths, and in the case of a film, the resin composition is sandwiched and overlapped with another cloth and heated and fused. Then, in the case of heat fusion, at a temperature of 90 to 180 ° C., which is higher than the melting point of the resin composition, for 0.1 to 30 seconds, 0.1 to 2 kg /
The pressure may be increased by about ² cm ² . Further, as a heating and pressing method, a known method such as a hot press or a hot roll can be used.

The heat-adhesive laminate of the present invention obtained by laminating and fusing the resin composition on a fabric as described above has an extremely high adhesive strength to a wide variety of fabrics, and is excellent in water-washing resistance and dry-cleaning resistance. It is. This is considered to be due to the combined synergistic effect of each component constituting the resin composition in the present invention. If the action is presumed to be strong, the ethylene-based multi-component copolymer of the component (A) is a component for imparting a strong adhesive force to the fabric from the chemical properties of each component, and the polyolefin-based component of the component (B) The resin is a component for imparting dry cleaning resistance, and the EVA copolymer saponified component (C) is understood to have the properties of improving the strength and adhesion of the resin composition. The heat-adhesive laminate of the present invention can be used not only as an interlining for clothing, but also as a material for other materials such as a chair outer material, a waterproof sheet, a heat-adhesive label (for clothing), a resin adhesive cloth used for a cover, and the like. Can be provided.

[0016]

EXAMPLES The present invention is further described by Examples and Comparative Examples.
This will be specifically described. Example 1 As an ethylene-based multi-component copolymer, an ethylene-methyl methacrylate-maleic anhydride terpolymer was used. The terpolymer was prepared by using the equipment of a high-pressure low-density polyethylene plant at a polymerization temperature of 240 ° C. and a polymerization pressure of 1900.
It was manufactured under the condition of kg / cm ² . M of this terpolymer
FR (measured under JIS-K7210, Table 1, Condition 4, hereinafter MFR uses all these conditions): 9 g / 10 min, unit derived from methyl methacrylate 8% by weight, unit derived from maleic anhydride Was 3% by weight. The composition of the comonomer was determined by an infrared absorption spectrum method. Further, as a polyolefin-based resin, Shourex L170, a high-pressure low-density polyethylene [manufactured by Showa Denko KK, MFR = 7 g / 10 min, density = 0.917]
g / cc, melting point = 103 ° C.]. Further, as a saponified product of EVA, a commercial product having a melting point of 95 ° C. (ethylene content = 6)
9% by weight, saponification degree = 91%, MFR = 75 g / 10 min)
Was used. The mixing ratio of the above three components shown in Table 1,
That is, after the ethylene-based multi-component copolymer, the polyolefin-based resin combined, and the EVA saponified product were dry-blended at 65/25/10, a 37 mmφ co-directional twin-screw extruder was used.
The mixture was melt-kneaded at 0 ° C. to obtain pellets of the resin composition. Next, the obtained pellets were pulverized by a Wiley type pulverizer (manufactured by Yoshida Seisakusho), and an adhesion test was performed using a resin composition pulverized to 500 μm (35 mesh) or less by a classifier.
The adhesion test was performed using Tetron / cotton (65/35) broad for both the outer material and the interlining, and 50 g / m on the interlining.
^After spraying uniformly at the ratio of ^2, the outer material was overlaid, and in the low-temperature adhesion test, it was sandwiched between presses heated to 110 ° C. on the upper plate and 110 ° C. on the lower plate and pressed at a substantial surface pressure of 1 kg / cm ² for 3 seconds. The size of the fabric was 10 cm × 10 cm. After bonding, 23
15m after conditioning for 24 hours at 50 ℃ and 50% relative humidity
Cut into test pieces of m width, tensile speed 300m with tensile tester
A T-peel test (23 ° C.) was performed at m / min to measure the adhesive strength. The adhesive strength is an average value of five test pieces. In the high-temperature bonding test, the bonding strength was measured in the same manner except that the press temperature in the low-temperature bonding test was set to 130 ° C. Then, as a test for dry cleaning resistance, after pressing under the same conditions, immersed in a tetrachloroethylene solution at room temperature for 24 hours, the test specimen was visually observed,
What was lost from the fabric by dissolution of the resin composition was "x",
A resin composition almost remaining was evaluated as “残 っ”. Also, the test piece after immersion for 24 hours was washed with acetone,
After conditioning for 24 hours at 23 ° C. and 50% relative humidity, the adhesive strength was measured. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 2 Using the resin composition pellets prepared in Example 1, 45
A film having a thickness of 70 μm was formed using an inflation film forming machine having an extruder having a diameter of mmφ, and the film was opened to obtain a film having a width of 80 cm. Using this film, Tetoron / Cotton (65/35) Broad for both outer and interlining, layered interlining, adhesive film, and outer fabric in this order, and the low-temperature adhesion test was heated to 110 ° C for upper plate and 110 ° C for lower plate. Sandwiched between heat sealers, heat seal gauge pressure 2kg / c
and pressed in m ² 3 seconds. The size of the fabric is 10cm x 10
cm. After bonding, the condition was adjusted at 23 ° C. and a relative humidity of 50% for 24 hours, and then the bonding strength was measured in the same manner as in Example 1. In the high-temperature bonding test, the pressing temperature was set at 1
The adhesive strength was measured in the same manner except that the temperature was 30 ° C.
Then, the dry cleaning resistance test was evaluated in the same manner as in Example 1. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 3 Using the pellets of the resin composition prepared in Example 1, 25
A lamination laminate of the resin composition was obtained using a lamination film forming machine having an extruder of mmφ using Tetron / cotton (65/35) broad as an interlining.
Using this laminate, a resin surface was superimposed on Tetron / cotton broad, adhered in the same manner as in Example 2, and evaluated for quality. Workability was good, and adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 4 As an ethylene-based multi-component copolymer, the MFR was 100 g / 1.
For 0 minutes, a terpolymer was used in which the unit derived from methyl methacrylate was 8% by weight and the unit derived from maleic anhydride was 3% by weight. In addition, as a polyolefin resin,
SHYOUREX M25, a high-pressure low-density polyethylene
1 [manufactured by Showa Denko KK, MFR = 50 g / 10 min, density = 0.916 g / cc, melting point = 100 ° C.] Further, the same saponified EVA as in Example 1 was used. The following three components were used in the same manner as in Example 1 except that the mixing ratios shown in Table 1 were changed, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin combined, and the EVA saponified product were 60/35/5. It was measured. However, wool gabardine was used for the outer material and lining. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 5 An ethylene-based multi-component copolymer having an MFR of 11 g / 10
A terpolymer having 18% by weight of units derived from methacrylic acid and 2.6% by weight of units derived from maleic anhydride was used. Further, as a polyolefin-based resin, Shourex M251, a high-pressure low-density polyethylene (manufactured by Showa Denko KK, MFR = 50 g / 10 min, density = 0.9)
16 g / cc, melting point = 100 ° C.]. Furthermore, EV
A saponified product having a melting point of 102 ° C. (ethylene content = 67% by weight, saponification degree = 98%, MFR = 15 g /
10 minutes). The above three components were measured in the same manner as in Example 2 except that the mixing ratio shown in Table 1 was used, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin and the EVA saponified product were 25/70/5. did. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 6 As an ethylene-based multi-component copolymer, the MFR was 100 g / 1.
At 0 minutes, a terpolymer was used in which the unit derived from methyl methacrylate was 8% by weight and the unit derived from maleic anhydride was 2.6% by weight. Also, as a polyolefin-based resin, Shourex M, which is a high-pressure low-density polyethylene,
251 [manufactured by Showa Denko KK, MFR = 50 g / 10 min,
Density = 0.916 g / cc, melting point = 100 ° C.].
Further, the same as in Example 1 was used as the saponified EVA. The above three components were measured in the same manner as in Example 2 except that the mixing ratio shown in Table 1 was changed, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin and the EVA saponified product were changed to 50/15/35. did. Workability is very good,
The adhesive strength and dry cleaning resistance were also good.
Table 2 shows the measurement results.

Example 7 Example 6 was repeated except that wool gabardine was used for the outer material and the lining.
The measurement was carried out in the same manner as in Example 2 using the resin composition of Example 1.
The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 8 As an ethylene-based multi-component copolymer, the MFR was 100 g / 1.
At 0 minutes, a terpolymer was used in which the unit derived from methacrylamide was 8% by weight and the unit derived from maleic anhydride was 3% by weight. In addition, as a polyolefin resin,
SHYOUREX M25, a high-pressure low-density polyethylene
1 [manufactured by Showa Denko KK, MFR = 50 g / 10 min, density = 0.916 g / cc, melting point = 100 ° C.] Further, the same EVA saponified product as in Example 5 was used. The above three components were measured in the same manner as in Example 2 except that the mixing ratio shown in Table 1 was used, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin, and the EVA saponified product were 60/35/5. did. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 9 As an ethylene-based multi-component copolymer, the MFR was 100 g / 1.
At 0 minutes, a terpolymer was used in which the unit derived from methyl methacrylate was 8% by weight and the unit derived from maleic anhydride was 2.4% by weight. In addition, as a polyolefin resin, Showa Rex 1 which is a linear low-density polyethylene is used.
25J [Showa Denko KK, MFR = 50g / 10min,
Density = 0.915 g / cc, melting point = 120 ° C.].
Further, the same as in Example 1 was used as the saponified EVA. The above three components were measured in the same manner as in Example 2 except that the mixing ratios shown in Table 1 were used, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin and the EVA saponified product were 50/40/10. did. Workability is very good,
The adhesive strength and dry cleaning resistance were also good.
Table 2 shows the measurement results.

Example 10 As an ethylene-based multi-component copolymer, the MFR was 100 g / 1.
At 0 minutes, a terpolymer was used in which the unit derived from methyl methacrylate was 8% by weight and the unit derived from maleic anhydride was 2.4% by weight. Further, as a polyolefin-based resin, ethylene aroma copolymer MD770H [manufactured by Showa Denko KK, MFR = 3]
0 g / 10 min, ethylene copolymer = 7% by weight, melting point =
135 ° C]. Further, the same as in Example 1 was used as the saponified EVA. The above three components were mixed in the proportions shown in Table 1, ie, an ethylene-based multi-component copolymer, a polyolefin-based resin and an EVA saponified product in a ratio of 40/40/20.
The measurement was carried out in the same manner as in Example 2 except for the following. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. Table 2 shows the measurement results.

Example 11 As an ethylene-based multi-component copolymer, MFR was 8 g / 10
A terpolymer having 18% by weight of units derived from butyl methacrylate and 1.3% by weight of units derived from maleic anhydride was used. Also, as a polyolefin-based resin, Shourex M, which is a high-pressure low-density polyethylene,
251 [manufactured by Showa Denko KK, MFR = 50 g / 10 min,
Density = 0.916 g / cc, melting point = 100 ° C.].
Further, the same as in Example 1 was used as the saponified EVA. The above three components were measured in the same manner as in Example 2 except that the mixing ratio shown in Table 1 was used, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin and the EVA saponified product were 70/15/15. did. Workability is very good,
The adhesive strength and dry cleaning resistance were also good.
Table 2 shows the measurement results.

Example 12 An ethylene-based multi-component copolymer having an MFR of 9.2 g / 10
For example, a terpolymer containing 10.2% by weight of units derived from methyl methacrylate and 4.6% by weight of units derived from maleic anhydride was used. Also, as a polyolefin-based resin, Shourex M, which is a high-pressure low-density polyethylene,
251 [manufactured by Showa Denko KK, MFR = 50 g / 10 min,
Density = 0.916 g / cc, melting point = 100 ° C.].
Further, the same EVA saponified product as in Example 5 was used. The above three components were measured in the same manner as in Example 2 except that the mixing ratio shown in Table 1 was used, that is, the ethylene-based multi-component copolymer, the polyolefin-based resin and the EVA saponified product were 40/40/20. did. Workability is very good,
The adhesive strength and dry cleaning resistance were also good.
Table 2 shows the measurement results.

Comparative Example 1 The measurement was carried out in the same manner as in Example 2 except that the polyolefin resin was not used. The adhesive strength was good and the washability was good, but dry cleaning resistance was not obtained. Table 2 shows the measurement results.

Comparative Example 2 The measurement was carried out in the same manner as in Example 4 except that the saponified product of EVA was not used. The initial adhesive strength was low, and the adhesive strength after the dry cleaning resistance test was significantly reduced. Table 2 shows the measurement results.

Comparative Example 3 In Example 4, instead of the ethylene-based multi-component copolymer,
Example 4 was repeated except that an ethylene-vinyl acetate copolymer (MFR: 12 g / 10 min, units derived from vinyl acetate: 15% by weight) was used as the ethylene-based copolymer.
The measurement was performed in the same manner as described above. The initial adhesive strength was low and dry cleaning resistance was not obtained. The measurement result is
It is shown in the table.

Comparative Example 4 The measurement was carried out in the same manner as in Example 5 except that the ethylene-based multi-component copolymer was not used. The initial adhesive strength was low, and the adhesive strength after the dry cleaning resistance test was also low. Table 2 shows the measurement results.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

As described above, according to the present invention, a resin composition containing a specific ethylene-based multi-component copolymer, a polyolefin-based resin and a saponified EVA as a main component is laminated and fused to a fabric, thereby obtaining an adhesive. It is possible to obtain a heat-adhesive laminate having excellent strength, and excellent water-washing resistance and dry-cleaning resistance. Therefore, the heat-adhesive laminate of the present invention, interlining such as collars and cuffs, chair surface material, waterproof sheet,
It is effectively used as a material for thermal adhesive labels (such as clothing) and other covers.

(56) References JP-A-5-138831 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 7/00-7 / 04 C09J 123/00-123/08 D06M 17/00-17/10 A41B 3/06

Claims (5)

(57) [Claims] 1. A multi-component copolymer comprising (A) ethylene, a radical-polymerizable acid anhydride and another radical-polymerizable comonomer, wherein the radical-polymerizable acid anhydride in the ethylene-based multi-component copolymer is Derived unit ratio is 0.1 to 5
10 to 90% by weight of an ethylene-based multi-component copolymer in which the ratio of units derived from other radically polymerizable comonomers is 3 to 50% by weight, and (B) a polyolefin-based resin 10
A heat-adhesive laminate obtained by laminating and fusing a resin composition comprising from 90 to 90% by weight and (C) 1 to 40% by weight of a saponified ethylene-vinyl acetate copolymer to a fabric. 2. The resin composition according to claim 1, which is substantially solid, is laminated on a fabric, and then heated and pressed to a temperature higher than the melting point of the resin composition to impregnate the fabric. A method for producing a heat-adhesive laminate. 3. The method according to claim 2, wherein the resin composition is a powder having an average particle size of 500 μm or less. 4. The method according to claim 2, wherein the resin composition is a film having a thickness of 10 to 500 μm. 5. A method for producing a heat-adhesive laminate, wherein the resin composition according to claim 1 is coated on a fabric in a molten state, heated and pressed to impregnate the fabric.