JP2645622B2 - High-frequency fusing sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet material which can be subjected to high-frequency fusion, and is preferably used in a field requiring joining of sheet materials such as a shoe cover, a middle and a back, and a chair material. The present invention relates to the above-mentioned sheet material.

[0002]

2. Description of the Related Art At present, shoe shell materials, inner lining materials, sandals,
Chair materials, car interior materials and seat materials, handbags,
In other bags, cases, and the like, synthetic leather and other synthetic resin sheet materials are widely used, and these have a desired shape by joining the sheet materials.

For example, synthetic leather (a synthetic resin sheet having a urethane-based resin layer on a base cloth) is used as a covering material, and vinyl chloride leather (a synthetic resin sheet having a foamed vinyl chloride-based resin layer on a base cloth) is used as a medium. In a shoe used as a backing material, a shell material and a middle backing material are joined by a high-frequency welder at a peripheral portion of a shoe opening. In this case, calender molding is generally used for the vinyl chloride leather as the inner backing material. In addition, in addition to the above-mentioned high frequency welder, the joining between the shell covering material and the inner lining material at the peripheral portion of the wearing mouth is also based on the threading, but the finished appearance is inferior in the case of the threading. Above, it takes time to meet,
In addition, there is a drawback that the welded portion is frayed due to wearing for a long period of time, peeling or shape loss occurs, and recently, joining by a high frequency welder has been frequently used.

[0004] In recent years, interest in foot health has increased, and shoes have been demanded to have a good foot contact as a covering material, a middle lining material, and the like, and to be flexible to prevent valgus thumb. It is coming. In response to such a request, the above-described calender-molded vinyl chloride leather (hereinafter referred to as calendered vinyl leather) lacks flexibility, and therefore, is subjected to paste molding (a paste-like foamable vinyl chloride resin is applied on a base cloth). Attempts have also been made to use flexible vinyl chloride leather (hereinafter referred to as paste vinyl chloride leather) obtained by the above method as a middle backing material. However, paste PVC leather has low surface strength,
Not practical. Therefore, a technique has been developed in which a polyurethane coating layer is provided on the surface of the paste PVC leather to increase the surface strength of the leather. The paste PVC leather having the polyurethane coating layer replaces the above-described calender PVC leather and is used in shoes. It is being used as a backing.

[0005] Paste PVC leather having the above-mentioned polyurethane coating layer is not limited to the above-mentioned inner lining material of shoes, but may be, for example, handbags, bags, various kinds of bags, clothes, etc. Its use is expanding as well as used chair materials, car interior materials and seat materials.

[0006]

In the case of the paste vinyl chloride leather having the above-mentioned polyurethane coating layer, a two-pack type polyurethane adhesive is generally used when the polyurethane coating layer is provided. Originally, polyurethane is not very good in high-frequency fusion, and is affected by the curing agent of two-component polyurethane as an adhesive, and the polyurethane coating layer is further crosslinked, making it more difficult to perform high-frequency fusion. Become. In order to impart high frequency fusing properties to the paste PVC leather having the polyurethane coating layer, it is necessary to perform a surface treatment with a surface treatment agent made of polyvinyl chloride or the like. But,
When surface treatment is applied, not only the irregularities formed on the polyurethane coating layer become unclear, but also the number of steps increases, and the advantages of joining by a high-frequency welder, such as a good finished appearance and no trouble, are lost. There are drawbacks such as being rejected.

Therefore, the present inventors have tried to adhere the polyurethane coating layer to the paste vinyl chloride leather without using the above-mentioned polyurethane adhesive. However, in this case, since the polyurethane coating layer is in direct contact with the paste PVC leather, heat at the time of foaming the paste PVC into the coating layer is affected, and the surface of the polyurethane coating layer is roughened, which is a practical product. Was not obtained. On the other hand, it was considered to use a grade of polyurethane that does not cause surface roughness, but in such a grade of polyurethane,
High frequency welding was not possible at all. Under the circumstances described above, a fundamental solution that enables high-frequency fusion of the sheet itself is desired.

The present invention provides a high-frequency-fusible sheet material which has a soft touch, has a good touch, and can sufficiently respond to recent high-grade orientations without causing the above-mentioned problems. The purpose is to do.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted various studies in order to achieve the above-mentioned object. As a result, they have used an acrylic-urethane copolymer as a resin constituting a polyurethane coating layer. Polyurethane has a soft texture, good touch, and also has excellent high-frequency fusing properties, without causing the surface roughness of the paste PVC sheet and without causing adverse effects such as blurring the unevenness drawing, It has been found that it can be firmly bonded directly (without using an adhesive).

[0010] The sheet material capable of high-frequency fusion according to the present invention is based on the above findings, and is characterized in that a coating layer made of an acrylic-urethane copolymer is provided on a vinyl chloride resin sheet formed by paste molding. And

The acrylic-urethane copolymer in the sheet material of the present invention is a polyurethane into which an acrylic group has been introduced, and specifically refers to a copolymer of an acrylic compound, a polyol and a polyisocyanate.

The ratio of the acryl group to the polyurethane in the above copolymer is such that if the acryl group is too small, the sheet material of the present invention does not show high-frequency fusion property, and if the acryl group is too large, Not only is the effect of improving the high-frequency fusion property commensurate with that obtained, but the polyurethane content is relatively too small, and the toughness and wear resistance of the coating layer of the sheet material tend to decrease. Therefore, in the present invention, acrylic group: polyurethane = 1: 99 to 50:50 (% by weight),
Preferably, a ratio of 5:95 to 40:60 (% by weight) is suitable.

Examples of the acrylic compound include a hydroxyl group-containing acrylic monomer, acrylate and / or methacrylate, nitrile such as acrylonitrile and methacrylonitrile, amide such as acrylamide and methacrylamide, acrylic acid and methacryl. Acids such as acids can be used alone or in combination of two or more.

When such an acrylic monomer is used as a mixture, the composition may be such that 1 to 40 parts by weight of a hydroxyl group-containing acrylic monomer, 30 to 99 parts by weight of an acrylate ester and / or a methacrylate ester. Parts and the other copolymerizable monomer may be 0 to 60 parts by weight, and in any case, the composition of each monomer is adjusted so that the total amount of the monomer mixture becomes 100 parts by weight. What is necessary is just to determine a ratio.

As the hydroxyl group-containing acrylic monomer, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyisopropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyisopropyl methacrylate, 2-hydroxybutyl methacrylate , 2-hydroxypentyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerol methacrylate monoester, trimethylolpropane acrylate monoester or methacrylate monoester, or 2-hydroxy-3 -Chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate and the like.

Examples of the acrylate and / or methacrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Examples include 2-ethylhexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate.

Other monomers capable of copolymerization include:
Styrene or derivatives thereof such as styrene, α-methylstyrene, β-chlorostyrene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl isopropionate;
Acids such as fumaric acid, maleic acid and itaconic acid can be used.

As the polyisocyanate, for example,
Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate Examples thereof include aliphatic or alicyclic diisocyanates such as isocyanate, and these can be used alone or in combination of two or more.

Examples of the polyol include glycols having 4 or more carbon atoms such as 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol and fats such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. Polyester polyol obtained by condensation polymerization of dicarboxylic acid component such as aromatic dicarboxylic acid; lactone polyester polyol obtained by ring-opening polymerization of lactone such as ε-caprolactone, methylvalerolactone; dialkyl carbonate, diaryl carbonate, or alkylene Polycarbonate polyester polyol obtained by transesterification of a carbonate such as carbonate with a polyhydroxy compound; polypropylene ether glycol polyol, polytetramethylene ether glyco Le-based polyol can be used, in particular, polycarbonate-based polyester polyols are preferred. These polyols can be used alone or as a mixture of two or more.

As the dialkyl carbonate, diaryl carbonate, or alkylene carbonate as a raw material of the above-mentioned polycarbonate-based polyester polyol, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, di-iso-carbonate produced from phosgene as a starting material. Butyl carbonate, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,
2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-
Pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate and the like can be used.

Further, as the polyhydroxy compound,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 1,7-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-
Hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2
-Bis- (4-hydroxycyclohexyl) -propane, p-xylenediol, p-tetrachloroxylenediol, 1,4-dimethylolcyclohexane, bishydroxymethyltetrahydrofuran, di- (2-hydroxyethyl) dimethylhydantoin, diethylene glycol, Triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, thioglycol, trimethylolethane, trimethylolpropane,
Hexanetriol, pentaerythritol and the like can be used.

If necessary, a chain extender can be used. Examples of the chain extender include compounds having two active hydrogen atoms, such as ethylene glycol, propylene glycol, butanediol, hexanediol, and the like.
Diols such as -methyl-1,5-pentanediol, 1,4-cyclohexanediol, xylene glycol;
Diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, phenylenediamine, and tolylenediamine; dihydrazides such as hydrazine, adipic dihydrazide, and isophthalic dihydrazide; and the like, alone or in combination of two or more. It can also be used.

Specific products of the acryl-urethane copolymer of the present invention obtained from the above compounds include:
Product name “Rezamin ME3182LP” manufactured by Dainichi Seika Co., Ltd.
And "Resamine ME3820LP". These can be used alone or in a mixture at an appropriate ratio.

The thickness of each coating layer differs depending on the thickness of the paste-formed vinyl chloride resin sheet (hereinafter referred to as "paste PVC sheet") on which the coating layer is provided, and cannot be determined unconditionally. If too long, the sheet material of the present invention not only does not show high-frequency fusing properties, but also has no effect of improving surface strength, does not endure practical use, and conversely, is too thick,
Not only is the effect of improving the high-frequency fusion property corresponding thereto not obtained, but also the flexibility is reduced and the material cost is increased. Therefore,
In the sheet material of the present invention, the thickness of the paste PVC sheet is 0.1 mm.
For 1 to 2 mm, the thickness of the coating layer is 10 to 100 μm
It is preferable to use a ratio such that the ratio is a standard.

The above-mentioned paste PVC sheet provided with the coating layer refers to a sheet obtained by forming a paste in which a vinyl chloride resin is dispersed in a plasticizer into a sheet. Examples of the vinyl chloride resin include vinyl chloride homopolymer, copolymers of vinyl chloride and other monomers such as ethylene, vinyl acetate, vinyl ether, maleic ester, (meth) acrylic acid, and (meth) acrylic ester. These polymers may be used alone or in combination of two or more.

As the plasticizer for dispersing the above-mentioned vinyl chloride resin, any plasticizer can be used as long as it is used in ordinary vinyl chloride pastes. For example, phthalic acid derivatives such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, dibenzyl phthalate, dilauryl phthalate, didodecyl phthalate and diundecyl phthalate; phthalate acid derivatives such as diisodecyl phthalate and diisononyl phthalate; n
Adipic acid derivatives such as -butyl adipate and dioctyl adipate; maleic acid derivatives such as di-n-butyl malate; citric acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as monobutyl itaconate; Oleic acid derivatives; ricinoleic acid derivatives such as glycerin monocitrate; other tricresyl phosphate (TCP), trixylyl phosphate (TXP), dixylyl monocresyl phosphate (D
XMCP), monoxylyl dicresyl phosphate (M
XPCP) and the like, a phthalate ester-based plasticizer containing an epoxy group, an epoxidized soybean oil, an epoxy resin-based plasticizer, and the like. These may be used alone or in combination of two or more. Can also.

The above-mentioned vinyl chloride resin paste contains additives used in general paste-molded vinyl chloride resin sheet materials, such as foaming agents, stabilizers, antioxidants, coloring agents, and fillers. , A weather resistance improver, a thermal early coloring inhibitor, a light stabilizer and the like.

Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N'-dinitropentamethylenetetramine, benzenesulfonylhydrazide and the like.

As the stabilizer, barium stearate,
Zinc stearate, calcium stearate, barium ricinoleate, triphenyl phosphite, tris (nonylphenyl) phosphite, dioctyl nonyl phosphite, diphenyl acid phosphite, tri-n-
Dodecyl-trithiophosphite, phenyl-di-n-
Decyl phosphite, di-n-octadecyl-pentaerythritol diphosphite and the like can be mentioned.

As antioxidants, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,6-
Phenolic antioxidants such as di-t-butyl-p-cresol and 4,4'-thiobis- (3-methyl-6-t-butylphenol); di-n-dodecyl-thiodipropionate, di-n Thiodipropionic esters such as octadecyl-thiodipropionate; sulfides and disulfides such as di-n-dodecyl sulfide, di-n-octadecyl sulfide and di-n-octadecyl disulfide;

As fillers, silica, talc, calcium carbonate, magnesium carbonate, feldspar, quartz, hydrotalside compounds, aluminum hydroxide, magnesium sulfate, calcium phosphate, magnesium hydroxide, crosslinked vinyl chloride resin, crosslinked acrylic resin Resins.

Examples of the light stabilizer include hindered amine light stabilizers. Of course, compounds other than those exemplified here can also be added.

In order to produce the sheet material of the present invention comprising the above components, for example, first, a solvent solution of an acryl-urethane copolymer is applied on a release carrier, and this is dried and dried. A coating layer having the above thickness is formed. Next, the above-mentioned vinyl chloride-based resin paste is applied directly on the coating layer, that is, without the use of an adhesive, and gelled by heating,
Alternatively, foaming is performed after heat gelation to form a paste PVC sheet. Thereafter, it is only necessary to peel off the release carrier.

As the releasable carrier, in addition to release papers such as silicon paper whose surface is treated with silicon, those generally used as releasable carriers such as silicon paper can be preferably used. As the solvent, those generally used as solvents for polyurethane, such as methyl ethyl ketone, acetone, dimethylformamide, dimethylsulfamide, tetrahydrofuran, cyclohexanone, dioxane, and ethyl acetate, can be preferably used.

[0035]

The acrylic-urethane copolymer constituting the coating layer of the sheet material of the present invention has high-frequency fusing properties,
The adhesiveness to the paste PVC sheet is good, and a strong coating layer is formed on the paste PVC sheet without using an adhesive. Therefore, the sheet material of the present invention is capable of high-frequency fusion, and furthermore has the disadvantages of the paste polyvinyl chloride leather having a polyurethane coating layer that required the use of a conventional two-component polyurethane adhesive, namely Further, no further cross-linking of the coating layer occurs due to the effect of the curing agent of the two-component polyurethane adhesive, and the high-frequency fusion property does not disappear with this.

The sheet material of the present invention maintains excellent flexibility by the paste PVC sheet, and the surface strength of the paste PVC sheet is ensured by the coating layer. Further, by the synergistic action of the above-mentioned paste PVC sheet and the above-mentioned coating layer, various articles prepared by high-frequency fusion using the sheet material of the present invention as a material have a good finished appearance and a long appearance. It should be free from exfoliation and shape loss even when used for a period of time, and be flexible, have excellent texture and feel, and sufficiently respond to recent high-grade orientation.

[0037]

【Example】

Example 1 A solvent solution of an acrylic-urethane copolymer having the composition shown in Table 1 was applied to a surface of silicon paper having a natural leather-like unevenness on the surface so as to have a dry thickness of 10 μm. Was dried at 130 ° C. for 2 minutes to form a coating layer. On this coating layer, a vinyl chloride-based resin paste having the composition shown in Table 1 was applied so as to have a dry thickness of 0.15 mm, and this was gelled at 140 ° C. for 1 minute, and then 190 ° C.
For 1.5 minutes to form a paste PVC sheet. Thereafter, the silicon paper was peeled off, and a sheet material of the present invention having a natural leather-like constriction on the surface was obtained.

[0038]

[Table 1]

This sheet material was used as the inner backing cloth of a shoe, and bonded to a synthetic leather upper covering material with a high frequency welder to prepare a shoe upper covering. The shoes manufactured using the upper cover had a beautiful finish at the mouth portion, the softness of the entire inner lining cloth including the portion, and the sense of quality. When the new shoes were worn for a long time, no shoe rubbing occurred. When the shoes were put on and taken off at a rate of about 200 times a day for one month, no delamination was observed in any part of the shoes as well as in the mouth parts.

COMPARATIVE EXAMPLES 1-4 As a middle backing cloth, calendered vinyl chloride leather (Comparative Example 1), paste vinyl chloride leather (Comparative Example 2), polyester polyol obtained by reacting 1,4-butanediol with adipic acid were used. Paste vinyl chloride leather having a polyurethane coating layer obtained by reacting with diphenylmethane diisocyanate (Comparative Example 3), and surface treatment of the paste vinyl chloride leather having a polyurethane coating layer of Comparative Example 3 with a surface treatment agent comprising a vinyl chloride resin Four types of shoes were manufactured in the same manner as in Example 1 except that each of the shoes (Comparative Example 4) was used.

With respect to these four types of shoes, the same experiment as in Example 1 for rubbing and durability was performed. As a result, the shoe of Comparative Example 1 was durable, but lacked in flexibility, and slightly rubbed the shoe. The shoe of Comparative Example 2 had flexibility, but lacked durability, and peeled off at several places of the inner lining during long-time use. The shoes of Comparative Example 3 had considerable surface roughness and had no commercial value.
Therefore, instead of the above polyurethane, a grade of polyurethane having no surface roughness was used. However, since high-frequency fusion was extremely difficult, shoes were manufactured by using a thread. The finish at the mouth portion of the shoe was considerably inferior to the shoes of Example 1 and Comparative Examples 1, 2, and 4.
The shoe rubbing and durability were good. In the shoe of Comparative Example 4, high-frequency fusion was possible under the same conditions as in Example 1, and shoe rubbing and durability were good. However, the unevenness of the natural leather-like unevenness formed on the polyurethane coating layer was obtained. Disappeared and lacked a sense of quality.

[0042]

As described above in detail, according to the sheet material of the present invention, high-frequency welding is possible and is extremely useful as a material for various articles requiring joining. Further, the sheet material of the present invention is obtained by combining two types of resin sheets without requiring an adhesive, and retains the properties of each resin sheet without being hindered by the action of the adhesive. Things. Therefore, the excellent flexibility, texture, touch, high-grade feeling, etc. of the paste PVC sheet and the excellent high-frequency fusion property, surface strength, etc. of the acrylic-urethane copolymer as the coating layer can be provided as they are.

Claims (1)

(57) [Claims] 1. A high-frequency fusing sheet material comprising a vinyl chloride resin sheet formed by paste molding and a coating layer made of an acrylic-urethane copolymer provided thereon.