JPH0631848A - Heat bonding laminate and preparation thereof - Google Patents

Abstract

PURPOSE:To improve adhesive strength and water and washing resistance by laminating and welding a resin compsn. consisting of an ethylenic multi- copolymer each with a specified ratio of a radically polymerizable acid anhydride and other radically polymerizable comonomer and a polyolefin resin and a nylon copolymer with a specified amt. on a fabric. CONSTITUTION:A resin compsn. consisting of 10-90wt.% ethylenlc multi- copolymer with a ratio of the unit derived from a radically polymerizable acid anhydride of 0.1-5wt.% and with a ratio of the unit derived from other radically polymerizable comonomer of 3-50wt.% and 10-90wt.% polyolefin resin and 1-50wt.% nylon copolymer to 100 parts by wt. sum of both these ingredients, is bonded and welded on a fabric. For mixing of ingredients, for example there exist e.g. a method wherein the ingredients are dissolved in a solvent and are reprecipitated and a method wherein the ingredients are mixed under a molten condition.

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a heat-adhesive laminate and a method for producing the same, and more specifically, it can be used as an interlining material such as a collar or cuff, a chair outer material, a waterproof sheet, a heat-adhesive label (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 Ethylene-vinyl acetate copolymer (EVA) has been the main hot-melt adhesive conventionally used for clothing-related materials (for example, interlining), but it has low adhesive strength. Since the dry cleaning resistance is very poor, the range of use was naturally limited. In order to improve this, for example, EVA is completely saponified or partially saponified, or acrylic acid, maleic acid or the like is graft-polymerized to the saponified EVA, and
A polymer in which EVA is modified and modified by a method of introducing a carboxyl group by reacting a part of hydroxyl groups in the molecule of the saponified A with a dicarboxylic acid is also used. By the modification method of introducing such a polar group, the adhesive force is considerably improved, but the solvent resistance (dry cleaning resistance) is not yet sufficiently improved. Garments made using such an adhesive have the drawback that when dry-cleaned, the adhesive swells with a solvent such as perchlorethylene, causing the adhered cloth to partly peel off.
Polyamide-based adhesives, which have relatively high adhesive strength, are also used, but due to their high water absorption, water-washing resistance is poor, and resin bleeding, etc. occurs during adhesive pressing, resulting in sewn products. Has a drawback that the appearance is deteriorated, the texture of the fabric is impaired because the resin itself is too hard, and the cost becomes extremely high. In addition to these, polyester adhesives are also used, but those that mainly consist of polyester fibers have strong adhesive strength, but the adhesive strength to cloths made of other types of natural fibers or synthetic fibers, washing resistance This adhesive has a limited range of use, because its adhesiveness has not yet been obtained to be strong enough for practical use.

[0003]

At the present time, it has strong adhesiveness to a wide variety of fabrics, and also has excellent water-washing resistance and dry-cleaning resistance. In reality, inexpensive resin adhesive cloths used for waterproof sheets and other covers, heat-adhesive laminates and manufacturing methods thereof have not been established yet. The present invention provides a thermal adhesive laminate that solves these problems and a method for producing the thermal adhesive laminate.

[0004]

Therefore, the present inventors have
In view of the above situation, the inventors have earnestly conducted research to develop a heat-adhesive laminate that solves the drawbacks of the conventional method. As a result, by using a specific ethylene-based multi-component copolymer, a resin composition containing polyolefin resin and copolymerized nylon as a main component as an adhesive, it has a strong adhesive force to a wide variety of fabrics, Moreover, they have found that a heat-adhesive laminate having water-washing resistance and dry-cleaning resistance can be obtained. The present invention has been completed based on such findings. That is, the present invention provides an ethylene-based multi-component copolymer comprising (A) ethylene, a radical-polymerizable acid anhydride, and another radical-polymerizable comonomer other than the above, wherein the radical polymerization in the ethylene-based multi-component copolymer is performed. The ratio of the units derived from the acid anhydride is 0.1 to 5% by weight, and the ratio of the units derived from other radically polymerizable comonomer is 3 to 50% by weight.
10 to 90% by weight of the ethylene-based multi-component copolymer and 10 to 90% by weight of the (B) polyolefin-based resin, and (C) with respect to 100 parts by weight of the total amount of the components (A) and (B). The present invention provides a heat-adhesive laminate, comprising a resin composition comprising 1 to 50 parts by weight of copolymerized nylon, which is laminated and fused on a cloth.

The resin composition used for producing the heat-adhesive laminate of the present invention mainly comprises the above-mentioned (A) ethylene-based multi-component copolymer, (B) polyolefin-based resin and (C) copolymerized nylon. It is a component. First, in the present invention, the ethylene-based multi-component copolymer of the component (A) constituting the resin composition comprises ethylene, a radical-polymerizable acid anhydride, and a radical-polymerizable comonomer other than the radical-polymerizable acid anhydride. It is a copolymer. Here, the radical-polymerizable acid anhydride has one or more of each of a radical-polymerizable unsaturated bond and an acid anhydride group in the molecule, so that an acid anhydride group can be introduced into the molecule by polymerization. It is a compound. Specific examples of such a compound include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and a carbon number of at most 18. Examples thereof include alkadienyl succinic anhydride having a double bond at a terminal. These may be used alone or in combination of two or more kinds. Among these, maleic anhydride and itaconic anhydride are particularly preferable.

As the radical-polymerizable comonomer other than the above-mentioned radical-polymerizable acid anhydride, various compounds can be used. For example, an ethylenically unsaturated ester compound,
Examples thereof include an ethylenically unsaturated amide compound, an ethylenically unsaturated acid amide compound, an ethylenically unsaturated acid compound, an ethylenically unsaturated ether compound, and an ethylenically unsaturated hydrocarbon compound. Here, as the ethylenically unsaturated ester compound, specifically, for example, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate,
Examples thereof include propyl (meth) acrylate, butyl (meth) acrylate, 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, N-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. Further, as the ethylenically unsaturated acid amide compound, (meth) acrylic acid amide, N-methyl (meth) acrylic acid amide, N, N-dimethyl (meth)
Examples thereof include acrylic acid amide, N-ethyl (meth) acrylic acid amide, N, N-diethyl (meth) acrylic acid amide, and the like. Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid. Furthermore, examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, and the like.
Examples of the ethylenically unsaturated hydrocarbon compound and other compounds include styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acrolein, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride and vinylidene chloride. These comonomers may be used alone or in combination of two or more kinds. And among these,
(Meth) acrylic acid esters, (meth) acrylic acid amide, (meth) acrylic acid and the like are used as particularly preferable compounds. However, acrylic acid may react with maleic anhydride depending on the conditions, so (meth)
Acrylic amide is preferred.

In the ethylene multicomponent copolymer (A), the proportion of the units derived from the radical-polymerizable acid anhydride is 0.1 to 5% by weight, and the units derived from other radical-polymerizable comonomers. The proportion of units is 3 to 50% by weight.
Here, if the ratio of the radical-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, if it exceeds 5% by weight, the compatibility with the polyolefin resin is deteriorated and the performance of the product is deteriorated, which is not preferable. And the ratio of other radically polymerizable comonomer is 3
When the content is less than wt%, the crystal melting point of the ethylene-based multi-component copolymer is not sufficiently lowered, and the low temperature adhesiveness which is a feature of the present invention cannot be exhibited. Further, when it exceeds 50% by weight,
The handling of the multi-component copolymer resin becomes difficult, and the heat resistance and dry cleaning resistance of the product deteriorate, which is not preferable.

In producing the ethylene-based multi-component copolymer, basically, ordinary low-density polyethylene production equipment and its technology can be used. Generally, it is produced by radical polymerization at a pressure of 700 to 3000 atm in a temperature range of 100 to 300 ° C. by a bulk polymerization method. Preferably, the polymerization pressure is 1000-250.
0 atm, and the polymerization temperature is an average temperature of 150 in the reactor.
˜270 ° C. If the polymerization pressure is less than 700 atm, the molecular weight of the polymer will be low, and the resin physical properties of the resin composition will deteriorate. Further, when it exceeds 3000 atm, it only increases the manufacturing cost and is substantially meaningless. If the average polymerization temperature is less than 100 ° C., the polymerization reaction will not be stable and the conversion rate to the copolymer will decrease, which is economically problematic. Also,
If it exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, there is a risk of a runaway reaction. A vessel type reactor is preferably used as the polymerization device. Particularly, since radical-polymerizable acid anhydrides have poor polymerization stability, a high degree of homogenization within the reactor is required. If necessary, a plurality of reactors may be connected in series or in parallel to carry out multistage polymerization. Further, by partitioning the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

The ethylene-based multi-component copolymer is produced in the presence of at least one free radical initiator under the above reaction conditions. Here, as the free radical initiator, specifically, for example, oxygen; dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, acetyl peroxide, i-butyryl. Diacyl peroxides such as luperoxide and octanoyl peroxide, peroxycarbonates such as di-i-propylperoxycarbonate and di-2-ethylhexylperoxycarbonate, t
-Butyl-peroxypivalate, peroxyesters such as t-butyl peroxylaurate, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 1,1-bis-t-butylperoxycyclohexane; 2,2 Examples thereof include peroxyketals such as -bis-t-butylperoxyoctane, hydroperoxides such as t-butylhydroperoxide and cumene hydroperoxide, and azo compounds such as 2,2-azo-i-butyronitrile. Further, in the polymerization, various chain transfer agents can be used as the molecular weight modifier. Specific examples of the chain transfer agent include olefins such as propylene, butene, and hexene,
Examples thereof include paraffins such as ethane, propane and butane, carbonyl compounds such as acetone, methyl ethyl ketone and methyl acetate, and aromatic hydrocarbons such as toluene, xylene and ethylbenzene. The thus-produced ethylene-based multi-component copolymer satisfying the above conditions melts at a relatively low temperature and is rich in physicochemical interactions and reactivity with various base materials, and therefore is used in the present invention. The resin composition to be used plays a large role in exhibiting high adhesive strength even at low temperature molding.

In the present invention, the polyolefin resin as the component (B) constituting the resin composition is, for example, high density polyethylene, low density polyethylene,
Polypropylene, polyisoprene, polybutene, poly-
3-methylbutene-1, poly-4-methylpentene-
1, a copolymer of polybutadiene and the constitutional unit of the above resin, for example, an ethylene-propylene copolymer; butene-
1,4-methylpentene-1; linear low-density polyethylene using hexene-1, octene-1 and the like as comonomers,
Examples thereof include a propylene-ethylene block copolymer or a mixture of these resins. These polyolefin-based resins are effective in imparting dry-cleaning resistance and adhesive force when used at high temperatures. Among these, a polyolefin resin having a melting point of 100 ° C. or higher is preferably used from the viewpoint of dry cleaning resistance. If the melting point is less than 100 ° C, the dry cleaning resistance and the adhesive strength during high temperature use are not sufficient. Here, the melting point is DSC (Differential Scanning Calorimeter), D
It is a melting peak temperature measured by a device such as TA (Differential Thermal Analysis).

Further, in the present invention, there are various types of copolymerized nylon as the component (C) which constitutes the resin composition, but a higher nylon salt having 10 or more carbon atoms, ω
-Nylon containing structures derived from amino acids or lactams. Specifically, for example, nylon 6/66 copolymer, nylon 6/12 copolymer, nylon 66/12 copolymer, nylon 6/66/610 copolymer, nylon 6/66/12 copolymer, Nylon 6/612/12 Copolymer, Nylon 6/610/12 Copolymer, Nylon 6/66/11 Copolymer, Nylon 6/66/610 /
12 copolymers and the like. These copolymerized nylons are composed of the ethylene-based multicomponent copolymer (A) and (B).
It has an effect of further improving the adhesive force as compared with a resin composition composed of two components of a component polyolefin resin.

In the present invention, the resin composition is composed mainly of the above-mentioned components (A), (B) and (C). And the mixing ratio of each component is
(A) Component ethylene multi-component copolymer 10 to 90% by weight, preferably 20 to 70% by weight and (B) Component polyolefin resin 90 to 10% by weight, preferably 80 to
30% by weight, and total of component (A) and component (B) 1
To 100 parts by weight of component (C), copolymerized nylon 1 to 1
It comprises 50 parts by weight, preferably 5-40 parts by weight. Here, when the copolymerized nylon of the component (C) is less than 1 part by weight,
The effect of improving the adhesive strength cannot be expected. On the other hand, if it exceeds 50 parts by weight, it is no longer effective for improving the adhesive strength, and it is not economical because the copolymerized nylon is expensive. The resin composition of the present invention as described above is excellent in that it is strongly bonded by heat treatment at a relatively low temperature and at the same time, it retains the adhesive strength at a high temperature.

In the present invention, the resin composition is prepared by mixing the above-mentioned components (A), (B) and (C) as main components, and mixing the respective components according to their respective blending ratios. Various commonly known methods can be used for mixing the components. Specifically, for example,
A method of dissolving and reprecipitating each component in a solvent such as hot toluene, a method of mixing each component in a molten state, that is, a commonly used pressure kneader, roll, Banbury mixer, static mixer, screw type A method using an extruder or the like may be used. In some cases, the components may be dry blended to form a composition during molding. Then, in the present invention, the resin composition, if necessary, within a range not impairing the object of the present invention,
In addition to the components (A), (B) and (C), various additives, compounding agents, fillers and the like can be compounded. Specifically, for example, antioxidants (heat resistance stability), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), inorganic materials such as glass fillers. Examples include fillers, organic fillers, reinforcing agents, colorants (dyes and pigments), foaming agents, and fragrances.

The heat-adhesive laminate of the present invention is produced by using the above resin composition and laminating it on a cloth by various methods. Here, in most cases, the resin composition is obtained in a substantially solid state, and after being laminated on the fabric according to each application method, the fabric is impregnated by heating and pressing at a temperature higher than the melting point of the resin composition. The thermoadhesive laminate of the present invention is obtained. For example, when it is used as a powder, it is crushed by an appropriate crushing device, for example, a freeze crusher, and used as a powder having an average particle size of 500 μm (35 mesh) or less by a classifier. In this case, for example, if particles having an average particle size of more than 800 μm exceed 10%, it becomes difficult to uniformly mix these resin powders in the fine mesh of the cloth, and a sufficient effect cannot be obtained. When it is used as a film, it is formed into a film having a thickness of 10 to 500 μm by inflation molding, T-die molding or the like, and then laminated on a cloth. Here, if the thickness of the film 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, or the like in a molten state. In this case, the thickness of the melt coat layer is preferably 10 to 500 μm.
When the thickness is less than 10 μm, the adhesive strength is insufficient, and when it exceeds 500 μm, it may be exuded to the surface through the texture, which is not preferable. The resin composition thus laminated on the cloth is then impregnated into the cloth with an iron, a press, or the like to obtain a heat-adhesive laminate that can be used as a glued interlining material.

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 acrylics, recycled fibers such as rayon and acetate, inorganic fibers such as glass, natural fibers such as cotton, hemp, silk, and wool, and various fabrics made by mixing these Is mentioned. In addition, as the cloth, known materials such as woven fabric, knitted fabric, and non-woven fabric can be arbitrarily selected. As described above, the resin composition is sprinkled on the cloth in the case of powder, sandwiched in the case of film, and heat-fused together with other cloth. In the case of heat fusion, the melting point of the resin composition is 90 to
It may be carried out at 180 ° C. for 1 to 30 seconds while applying a pressure of about 0.1 to ² kg / cm ² . As a heating and pressurizing 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 fusion-bonding the resin composition onto a fabric in this manner has extremely high adhesive strength to a wide variety of fabrics and is excellent in water-washing resistance and dry cleaning resistance. is there. In the present invention, this is
It is judged that it is due to the total synergistic effect of each component constituting the resin composition. Estimating its action by force, the ethylene-based multi-component copolymer is a component that imparts a strong adhesive force to the fabric from the chemical properties of each component, and the polyolefin resin is a component that imparts dry cleaning resistance. It is understood that the copolymerized nylon, which is a component of 1., has the properties of improving the strength and adhesive strength of the resin composition. The heat-adhesive laminate of the present invention can be used not only as an interlining material but also as a chair outer material, a waterproof sheet, a heat-adhesive label (for clothing),
It can be used as a material such as a resin adhesive cloth used for a cover or the like.

[0017]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
A more specific description will be given. Example 1 As the ethylene-based multi-component copolymer, an ethylene-methyl methacrylate-maleic anhydride terpolymer was used. This ethylene-based terpolymer was produced under the conditions of a polymerization temperature of 240 ° C. and a polymerization pressure of 1900 kg / cm ² using the equipment of a high-pressure low-density polyethylene plant. MFR of the terpolymer (measured in JIS-K7210, Table 1, Condition 4; hereinafter, all MFR uses this condition) is 9 g / 1.
At 0 minutes, the content of units derived from methyl methacrylate was 8% by weight, and the content of units derived from maleic anhydride was 3% by weight. The composition of the comonomer was determined by infrared absorption spectrum. On the other hand, as a polyolefin-based resin, a high-pressure low-density polyethylene, Syolex L170 [trade name, manufactured by Showa Denko KK, MFR = 7 g /
10 minutes, density = 0.917 g / cc, melting point = 103 ° C.) were used. A commercially available product [manufactured by Fuji Kasei Kogyo KK, softening point 135 ° C.] was used as the copolymerized nylon. The above three components are mixed in the mixing ratios shown in Table 1, that is, ethylene terpolymer, polyethylene and copolymer nylon are 65/2.
37mm after dry blending at a mixing ratio of 5/10
Melt kneading was performed at 180 ° C. using a φ-screw twin-screw extruder to obtain pellets of the resin composition. Next, the obtained pellets were crushed by a Willey crusher (manufactured by Yoshida Seisakusho), and then an adhesion test was performed using a resin composition crushed by a classifier to 500 μm (35 mesh) or less. For the adhesion test, Tetoron / Cotton (65/35) broad was used for both the surface and the interlining, and evenly sprayed at a rate of 50 g / m ² on the interlining, and then the surface was overlaid. It is sandwiched between presses heated to 110 ° C and lower plate 110 ° C, and the actual surface pressure is 1 kg /
It was pressure-bonded for 3 seconds at cm ² . The size of the press plate is 10 cm
It was set to × 10 cm. After bonding, after conditioning for 24 hours at 23 ° C. and 50% relative humidity, cut into 15 mm width test pieces, and perform a T-type peel test (23 ° C.) at a tensile speed of 300 mm / min with a tensile tester to determine the adhesive strength It was measured. The adhesive strength is an average value of 5 test pieces. Also, the high temperature test
Except that the pressing temperature of the low temperature test was 130 ° C,
The adhesive strength was measured in the same manner. Then, as a dry cleaning resistance test, after pressing under the same conditions, after soaking in a tetrachlorethylene solution at room temperature for 24 hours, washing with acetone was performed at 23 ° C. and 50% relative humidity for 2 hours.
After conditioning for 4 hours, the adhesive strength was measured. That is, the test pieces were visually observed, and those in which the adhesive resin was dissolved and lost from the fabric were evaluated as "x", and those in which almost the adhesive resin remained were evaluated as "○". The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 2 Using the pellets of the resin composition prepared in Example 1, 45
The film is blown to a thickness of 70 μm with an inflation film molding machine having an extruder of mmφ and opened by opening 8
A 0 cm wide film was obtained. Using this film, Tetoron / Cotton (65/35) broad for both the surface and the interlining, the interlining, the adhesive film, and the surface were overlaid in this order. In the low-temperature adhesion test, the upper plate was heated to 110 ° C and the lower plate was heated to 110 ° C. Sandwiched between heat sealers, heat seal gauge pressure 2 kg / c
and pressed in m ² 3 seconds. Fabric size is 10 cm x 10
cm. After the bonding, the condition was adjusted for 24 hours at 23 ° C. and 50% relative humidity, and then the bonding strength was measured in the same manner as in Example 1. In addition, the dry cleaning resistance test was performed in the same manner as in Example 1 to evaluate the quality. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

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 molding machine having an extruder of mmφ and using Tetoron / cotton (65/35) broad as the interlining.
Using this laminate, the resin surface was laid over Tetoron / Cotton broad, adhered in the same manner as in Example 2, and the quality was evaluated. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 4 An ethylene-based multi-component copolymer having an MFR of 100 g / 1
0 minutes, the content of the unit derived from methyl methacrylate is 8% by weight, the unit derived from maleic anhydride is 3% by weight, and is a high-pressure low-density polyethylene as a polyolefin resin. X-Rex M251
[Product name, Showa Denko KK, MFR = 50g / 10
Min, density = 0.916 g / cc, melting point = 100 ° C.] and the same copolymer nylon as in Example 1 was used, and wool gabardine was used as the outer material and the inner material. The same procedure as in Example 1 was repeated except that the above three components were mixed in the mixing ratios shown in Table 1, that is, the mixing ratios of the ethylene-based terpolymer, polyethylene and copolymer nylon were 60/35/5. It was measured. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 5 An ethylene-based multi-component copolymer having an MFR of 11 g / 10
Min, the content of units derived from methacrylic acid is 18% by weight
And an ethylene-based terpolymer containing 0.6% by weight of a unit derived from maleic anhydride, and used as a polyolefin-based resin, is a high-pressure low-density polyethylene, Syolex M.
251 was used. Copolymerized nylon has a softening point of 1
A commercially available product (manufactured by Toray Industries, Inc.) at 00 ° C. was used. The above three components are mixed in the mixing ratio shown in Table 1, that is, a terpolymer,
The measurement was performed in the same manner as in Example 2 except that the mixing ratio of polyethylene and copolymer nylon was 25/70/5. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 6 An ethylene-based multi-component copolymer having an MFR of 10 g / 10
Of ethylene-based terpolymer containing 8% by weight of units derived from methyl methacrylate and 2.6% by weight of units derived from maleic anhydride. Polyethylene X-rayex M251 was used. As the copolymerized nylon, a commercially available product having a softening point of 120 ° C. (manufactured by Fuji Kasei Kogyo KK) was used.
The above three components were mixed in the mixing ratios shown in Table 1, that is, 55/1 of the terpolymer, polyethylene and copolymer nylon.
The measurement was performed in the same manner as in Example 2 except that the compounding ratio was 5/30. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2. Example 7 Measurements were performed in the same manner as in Example 2 except that wool gabardine was used as the outer material and interlining and the resin composition prepared in Example 6 was used. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 8 An ethylene-based multi-component copolymer having an MFR of 100 g / 1
At 0 minutes, the content of the units derived from methacrylic acid amide was 8% by weight, and the units derived from maleic anhydride were 3% by weight. An ethylene terpolymer was used. The following was used. Further, the copolymerized nylon is obtained in Example 5
The same one was used. Except for the above three components having the compounding ratio shown in Table 1, that is, the compounding ratio of terpolymer, polyethylene and copolymer nylon of 60/35/5,
Thereafter, the measurement was performed in the same manner as in Example 2. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 9 As an ethylene-based multi-component copolymer, MFR was 100 g / 1
At 0 minutes, the content of units derived from methyl methacrylate was 8% by weight, and the units derived from maleic anhydride was 2.4% by weight. An ethylene terpolymer was used, and a linear resin was used as a polyolefin resin. Low-density polyethylene X-Rex 125J [trade name, Showa Denko KK, MFR = 50
g / 10 minutes, density = 0.915 g / cc, melting point = 100 ° C.]
Was used. The same nylon as in Example 1 was used. The above three components are mixed in the mixing ratios shown in Table 1,
That is, the measurement was performed in the same manner as in Example 2 except that the terpolymer, polyethylene and copolymer nylon were mixed at a compounding ratio of 58/40/2. The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 10 As an ethylene-based multi-component copolymer, MFR was 100 g / 1
At 0 minutes, the content of units derived from methyl methacrylate was 8% by weight, and the units derived from maleic anhydride was 2.4% by weight. An ethylene terpolymer was used. Random allomer MD770H [trade name, Showa Denko KK]
Manufactured by MFR = 30 g / 10 minutes, ethylene copolymerization rate = 7% by weight, melting point = 135 ° C.]. The same copolymer nylon as in Example 6 was used. The above three components
The measurement was performed in the same manner as in Example 2 except that the compounding ratio shown in Table 1, that is, the compounding ratio of the terpolymer, polyethylene and copolymer nylon was 40/40/20.
The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 11 An ethylene-based multi-component copolymer having an MFR of 8 g / 10
Of ethylene-based terpolymer containing 18% by weight of units derived from butyl methacrylate and 1.3% by weight of units derived from maleic anhydride. Polyethylene X-rayex M251 was used. The same nylon as in Example 1 was used. The following three components were measured in the same manner as in Example 2 except that the compounding ratio shown in Table 1, that is, the compounding ratio of the terpolymer, polyethylene and copolymer nylon was 80/15/5. . The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Example 12 An ethylene-based multi-component copolymer having an MFR of 9.2 g / 10
Min, the content of units derived from methyl methacrylate is 10.2
% By weight, 4.6% by weight of units derived from maleic anhydride
The ethylene-based terpolymer of Example 1 was used, and as the polyolefin-based resin, the high-pressure low-density polyethylene Syolex M251 was used. The same copolymer nylon as in Example 6 was used. The following three components were measured in the same manner as in Example 2 except that the compounding ratio shown in Table 1, that is, the compounding ratio of the terpolymer, polyethylene and copolymerized nylon was 15/80/5. . The workability was very good, and the adhesive strength and dry cleaning resistance were also good. The measurement results are shown in Table 2.

Comparative Example 1 The measurement was performed in the same manner as in Example 2 except that the polyolefin resin was not used. The adhesive strength was good and the washing property was also good, but the dry cleaning resistance was not obtained. The measurement results are shown in Table 2. Comparative Example 2 The measurement was performed in the same manner as in Example 4 except that the copolymerized nylon was not used. Although there was no problem in the initial adhesive strength, the adhesive strength after the dry cleaning resistance test was significantly reduced. The measurement results are shown in Table 2.

Comparative Example 3 Instead of the ethylene-based terpolymer used in Example 4, an ethylene-based terpolymer having an MFR of 12 g / 10 min and a vinyl acetate-derived unit content of 15% by weight. Then, the measurement was performed in the same manner as in Example 4 except that was used. The initial adhesive strength was low, and the adhesive strength after the dry cleaning resistance test was significantly reduced. The measurement results are shown in Table 2. Comparative Example 4 The measurement was performed in the same manner as in Example 5 except that the ethylene terpolymer was not used in Example 5. The initial adhesive strength was low and the dry cleaning test resistance was not obtained. The measurement results are shown in Table 2.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

As described above, according to the present invention, a resin composition containing a specific ethylene-based terpolymer, a polyolefin-based resin and copolymerized nylon as the main components is laminated on a fabric and fused to form an adhesive. It is possible to obtain a heat-adhesive laminate having excellent strength as well as water-washing resistance and dry cleaning resistance. Therefore, the heat-adhesive laminate of the present invention includes an interlining material such as a collar and a cuff, a chair outer material, a waterproof sheet,
It is effectively used as a material for thermal adhesive labels (clothing etc.) and other covers.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuaki Tsutsumi 2 Nakanosu, Oita City, Oita Prefecture Showa Denko Oita Factory

Claims (5)

[Claims] 1. An ethylene-based multi-component copolymer comprising (A) ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the above, wherein the radical-polymerizable polymer in the ethylene-based multi-component copolymer is used. 10 to 90% by weight of an ethylene-based multi-component copolymer in which the proportion of units derived from an acid anhydride is 0.1 to 5% by weight, and the proportion of units derived from another radical-polymerizable comonomer is 3 to 50% by weight, and (B) Polyolefin resin 90 to 10% by weight, and (C) with respect to 100 parts by weight of the total amount of the components (A) and (B).
A heat-adhesive laminate, comprising a resin composition comprising 1 to 50 parts by weight of copolymerized nylon, which is laminated and fused on a cloth. 2. The resin composition according to claim 1, which is substantially solid, is laminated on a cloth, and is then heated and pressurized to a temperature equal to or higher than the melting point of the resin composition to impregnate the cloth. A method for producing a heat-adhesive laminate. 3. The method for producing a heat-adhesive laminate according to claim 2, wherein the resin composition is a powder having an average particle size of 500 μm or less. 4. The method for producing a heat-adhesive laminate 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, which comprises coating a fabric with the resin composition according to claim 1 in a molten state and impregnating the fabric.