JP2604428B2 - Multi-layer body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is a multilayer body obtained by laminating a layer of a polyvinyl chloride resin and a layer of a fibrous structure via an adhesive layer. In particular, the present invention relates to a multilayer body having extremely excellent adhesion, durability and feeling at low temperatures.

(Prior Art) For a plasticized polyvinyl chloride resin, the number of highly crystalline carbons such as polyethylene adipate, polybutylene adipate, polyhexylene adipate and the like is 6 in terms of adhesiveness, plasticizer transferability and the like. Polyurethane-based adhesives mainly composed of polyester starting from the following monomer diols have been used. Similarly, in a multilayer structure composed of a layer of a polyvinyl chloride resin and a layer of a fibrous structure, a polyester-polyurethane-based adhesive mainly composed of a polyester starting from a monomer diol having 6 or less carbon atoms is used. Have been.

(Problems to be Solved by the Invention) In recent years, higher grades of products have been pursued, for example, emphasis has been placed on the easiness of fashionability and the feeling of products has been valued. A polyester-polyurethane-based adhesive having a high crystallinity mainly composed of a polyester starting from a diol has a sufficient adhesiveness, but has a hard feeling and lacks a sense of quality as a commercial product, and has a practical problem. On the other hand, in order to form a multilayer structure composed of a layer of a polyvinyl chloride resin having a good feeling and a layer of a fibrous structure, a flexible adhesive must be used even at the expense of adhesive performance. In this case, not only is the adhesive performance inferior, but also
Various durability such as heat resistance, hydrolysis resistance, and heat and humidity resistance were not sufficient, which was a practical difficulty.

In view of the above current situation, the present inventors have a soft feeling and have extremely excellent normal adhesive strength, low temperature resistance, and excellent durability (water resistance, heat resistance, content resistance, bending resistance, etc.). In order to obtain a multilayer body in which a layer of the polyvinyl chloride resin and a layer of the fibrous structure were laminated via an adhesive layer, intensive studies were conducted.

(Means for Solving the Problems) The present inventors have paid attention to the basic structural unit of the polymer constituting the adhesive, and have studied a novel adhesive having a new basic structural unit. Surprisingly, when compared to a conventional polyester polyurethane resin having a diol residue having 6 or less carbon atoms as a constituent unit, a resin having a specific structure of a diol residue having 9 carbon atoms as a constituent unit is used as the adhesive layer. Has a soft feel and normal adhesion, low temperature resistance, durability (water resistance,
The present invention has been found to obtain a multilayer body in which a layer of a polyvinyl chloride resin excellent in content resistance, heat resistance, bending resistance, etc.) and a layer of a fibrous structure are laminated via an adhesive layer. It is a result.

(Detailed Description of the Invention) That is, the present invention relates to a multilayer body composed of a layer of a polyvinyl chloride resin and a layer of a fibrous structure, represented by the following formula (I) as a bifunctional alcohol component in the molecule as an intermediate layer. It is a multilayered layer characterized by interposing a resin mainly composed of a polymer containing structural units.

—OCH ₂ CH (CH ₃ ) (CH ₂ ) ₆ O— (I) The polymer is not particularly limited, but the polymer containing the structural unit represented by the formula (I) may be a diol residue represented by the formula (I) More preferably, it is composed of a polyester polyol (a) containing a structural unit represented by the formula (1) or a polyurethane polyol (b) of the polyol and an organic diisocyanate.

As the compound capable of forming the structural unit of the group represented by the formula (I) used in the present invention, 2-methyl-1,8-octanediol is preferable. Indicated by

 Hereinafter, these polymers will be described in detail.

In the above-mentioned polymer, the polyester polyol itself or the base is used. The polyester polyol (a) has the formula (I) in a molecule obtained from 2-methyl-1,8-octanediol and a dicarboxylic acid. And a compound preferably having a hydroxyl group or an isocyanate group at the molecular terminal. In addition,
A part of the diol residue represented by the above formula (I) may be replaced with another diol residue within a range not to impair the intended purpose of the present invention.

Substitutable diols include ethylene glycol, 1,
Examples thereof include diols having 2 to 12 carbon atoms such as 4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol and neopentyl glycol. In addition, the use of a small amount of a polyhydric alcohol such as trimethylolpropane, glycerin, and pentaerythritol may be used in combination with the diol. In any case, it is desirable that the structural unit [I] is at least 5 mol%, preferably at least 10 mol%, more preferably at least 20 mol% of the diol component.

The structural unit of the dicarboxylic acid used in combination with the diol represented by the formula (i) for producing the polyester polyol is represented by the following formula (II) However, dicarboxylic acid units represented by the following formula (III) can be used in combination.

In the above formula (II), n represents an integer of 1 to 12, and examples of the aliphatic dicarboxylic acid capable of forming the above formula include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecane diacid And the like. More preferred are adipic acid, azelaic acid and sebacic acid. These dicarboxylic acids may be used alone or in combination of two or more. In the formula (III), Ar is a divalent aromatic hydrocarbon residue having 6 to 10 carbon atoms, and the residue is, for example, a phenylene group or a naphthylene group. Specific examples of the resulting aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like, and any ratio thereof. Mixtures are mentioned. More preferred are terephthalic acid and isophthalic acid. Alkyl esters thereof can also be used as the aromatic dicarboxylic acids.

The method for producing the polyester polyol is not particularly limited, and known polyester condensation polymerization means can be applied. For example, the structural units [I], [II] and [III]
Is charged in the desired ratio, and in the presence of an esterification and / or transesterification catalyst, from 150 to 250
It can be produced by esterification or transesterification at ℃ and further subjecting the reaction product thus obtained to polycondensation at a high vacuum of 200 to 300 ° C.

When the polyester polyol is used as an adhesive as it is, or when the polyol is used in the form of a polyurethane polyol by reacting with an organic diisocyanate, or in the case of being used in the form of a polyurethane polyisocyanate, The average molecular weight is not particularly limited, but is generally in the range of 500 to 500,000.

The organic diisocyanate used for producing the polyurethane polyol (b) in the present invention includes a known aliphatic, alicyclic or aromatic organic polyisocyanate containing two isocyanate groups in a molecule. You. Specifically, for example, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hexamethidine diisocyanate, isophorone diisocyanate, 4,4'- And dicyclohexylmethane diisocyanate. In particular, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate or a mixture containing these as a main component is preferred. In addition to the above-mentioned organic diisocyanate, a small amount of a polyfunctional polyisocyanate such as trimethylolpropane or triisocyanate obtained by adding 3 mol of tolylene diisocyanate to 1 mol of glycerin can be used together.

At this time, if desired, a suitable chain extender may be used. Examples of the chain extender include a chain extender commonly used in the polyurethane industry, that is, a compound containing at least two hydrogen atoms capable of reacting with isocyanate. Included. Examples include ethylene glycol, 1,4-butanediol, 1,6-hexadiol, xylylene glycol, 3-methyl-1,5-pentanediol, bishydroxyethoxybenzene, neopentyl glycol,
Examples include 9-nonanediol, isophoronediamine, hydrazine, dihydrazide, trimethylolpropane, glycerin and the like. In addition, as for a specific operation method for obtaining the above polyurethane polyol, a known technique of a urethane reaction is used. For example, except that acetone is used as the solvent, the acid value measured according to JIS K0070 is 2 or less, more preferably 1.0 or 0.4 or less, and the hydroxyl value measured according to JIS K0070 is 11 to 30.
0, more preferably 35-200, even more preferably 45-130
And a low molecular weight compound having active hydrogen, if desired, and preheated to about 40 to 100 ° C., and the ratio of the isocyanate group to the number of active hydrogen atoms (NCO / OH) of these compounds is 1 or less. It is obtained by adding a certain amount of organic diisocyanate and reacting at 50 to 120 ° C. for several hours. The above reaction may be carried out in the presence of an organic solvent inert to the isocyanate group. If desired, conventional urethanization catalysts such as organic tin compounds, organic titanium compounds, tertiary amines and the like may be used. When the production process is carried out in the presence of an organic solvent, the solid content of the final mixture is about 10-90% by weight, preferably 20-80% by weight.
It is convenient to determine the amount of the organic solvent to be used so as to be% by weight.

The viscosity of the polyurethane polyol thus obtained is not particularly limited, but the viscosity at a concentration of 30% measured at 30 ° C. is usually 10 to 10 from the viewpoint of the manufacturing process of the laminated structure.
30,000 centipoise (cps) is used.

In the present invention, the polyester polyol (a) or the polyurethane polyol (b) as a polymer having a group represented by the formula (I) in the molecule preferably has at least two hydroxyl groups at the molecular terminals.

In the present invention, an adhesive can be used only with a polymer having a group represented by the formula (I) in the molecule. However, when improvement in heat resistance and hot water resistance is expected, the formula (I) It is preferable to use an adhesive comprising a polymer having a group represented by I) and a compound having at least three groups capable of reacting with a hydroxyl group in the polymer as a curing agent.

Examples of the curing agent used here include organic polyisocyanates, epoxy resins, and mixtures thereof, and organic polyisocyanates are particularly preferable. Preferred organic polyisocyanates include compounds having three or more isocyanate groups in the molecule, such as trimethylolpropane, glycerin, and all hydroxyl groups such as pentaerythritol. Compounds.

When a curing agent is used in the adhesive of the present invention, the mixing ratio of the main agent and the curing agent is not particularly limited, but is often 40 parts by weight or less per 100 parts by weight of the solid component of the main agent.

In the present invention, a resin mainly composed of a polymer containing a structural unit represented by the following formula (I) as a bifunctional alcohol component in the molecule can be used as it is as the intermediate layer.

_{-OCH 2 CH (CH 3) (} CH 2) 6 O- (I) applying a known formulation to be applied to polyurethane adhesives no problem does not impair the object of the present invention. Examples of such formulation include addition or grafting of a phosphorus compound, addition of an epoxy compound, addition of a silane coupling agent, and the like.

The thickness of the adhesive layer is not particularly limited, but is usually 0.2 to 200.
Micron, and more often 2-100 microns.

Polyvinyl chloride is obtained by radical polymerization of a vinyl chloride monomer by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc., and usually, a stabilizer is added to improve its thermal stability. I have. Metallic stabilizers include calcium, magnesium, barium, strontium,
Cadmium, zinc, tin, lead and other carboxylates, inorganic acid salts, alcoholates, phenolates, mercaptides, organometallic compounds, and the like. Examples include epoxy compounds and thioethers. Since polyvinyl chloride alone is rigid and its use is limited, it is used by adding various plasticizers. Examples of the plasticizer include di-n-octyl phthalate, di-n
-Butyl phthalate, di-2-ethyl phthalate, di-
n-decyl phthalate, tricresyl phosphate, triethyl phosphate, tri-2-ethylhexyl phosphate and the like are used. 5 stabilizer without plasticizer
There are hard polyvinyl chloride added with ７7% and soft polyvinyl chloride added with 1-3% of stabilizer and 30-70% of plasticizer. In the present invention, both hard polyvinyl chloride and soft polyvinyl chloride can be used, but soft polyvinyl chloride is more preferably used.

These resins may be previously formed into a film shape, a cylindrical shape, or the like. It is generally used in the form of sheets, films, leather, and extruded products. Although there is no particular limitation on the thickness of the resin layer, it is usually 10 microns to 2 mm, and even 15
Often used from microns to 5mm.

Natural fibers such as cotton, silk, hemp, wool, asbestos, regenerated fibers such as viscose rayon, copper ammonia rayon, semi-synthetic fibers such as acetate, etc.
Polyamide-based (nylon 6, nylon 66, aromatic nylon), polyvinyl alcohol-based, polyvinylidene chloride-based, polyester-based, polyacrylonitrile-based, polyurethane-based, and polyalkylene paraoxybenzoate-based synthetic fibers can be used. Cotton, polyamide (nylon 6, nylon 66, aromatic nylon),
Polyvinyl alcohol, polyester, polyurethane and the like are preferably used. The form of the synthetic fiber is not particularly limited. For example, any of so-called spun yarns obtained by spinning short fibers and so-called filaments, which are so-called filaments, can be used. Further, for example, various treatments such as false twisting may be performed. For natural yarn, for example, cotton yarn is not particularly limited, but usually 28 to 30
In many cases, number 0 is used. For synthetic fibers, there is no particular limitation on spun yarn, but single yarn denier is usually 0.5 to 3
It is often used at 0 denier, more preferably at 1 to 15 denier. Although there is no particular limitation on the multifilament, single-denier is usually used in a range of 0.5 to 30 denier. 25 to 1 to 15 denier monofilament
Often used as an aggregate of ~ 300. Also,
There is no particular limitation in monofilament, but it is often used at 50 to 4000 denier.

As the structure of the fibrous structure, so-called woven fabric, knitted fabric,
A two-dimensional or three-dimensional fiber aggregate known as a non-woven fabric is used. Among them, a woven fabric and a knitted fabric, and a woven fabric are particularly preferably used.

The woven fabric is formed from a warp and a weft,
The organization is based on the Mihara organization of plain weave, oblique and satin. The plain weave design means that the warp and the weft have a complete design with two each, and are alternately interlaced one by one. The oblique weave design is a combination of two or more warp yarns and weft yarns to represent a diagonal ridge, and three or more yarns with a complete design. In the satin weave design, the intersections are uniformly distributed at regular intervals, and the surface is mostly covered with either warp or weft. The one covered with warp is called warp, and the opposite is called wetsu. In the present invention, any fabric can be used without being limited to the fabric having the above-mentioned structure, but a fabric having a plain weave structure is particularly preferable.

If you show concrete examples, for example, sackcloth, thin cloth, gold cloth, muslin, gingham, poplin, broadcloth, taffeta, suka, shyantan, flat, diozzet,
Examples include denim, boiling, shear, surge, gear virgin, cashmere, tweed, and the like.

A knitted fabric is one that constitutes a cloth by a continuous stitch.
For example, there are a knitting machine with a horizontal knitting machine such as a flat knitting machine and a circular knitting machine, and a vertical knitting machine made with a tricot machine, a frassel machine, a Miranese machine or the like.

The nonwoven fabric is obtained by bonding fibers together by chemical means, mechanical means or both, and keeping the form without spinning, weaving or braiding. Treated under chemical or mechanical action or appropriate moisture and heat,
Fibers may be bonded together. Examples of dry nonwoven fabric include an adhesive type using a dipping method, a printing method, a spray method, a powder method, an adhesive fiber method, etc., a mechanical bonding type using a felt method, a needle punching method, a stitch method, etc., a spinning type using a short fiber method, a filament method, etc. Etc. Examples of the wet nonwoven fabric include a papermaking type using a fibrillation method, an adhesive fiber method, a hot pressure method, a solvent method, an adhesive method, and the like. Any type of nonwoven fabric may be used.

In the production of the multilayer structure, the fibrous structure layer formed in advance and the polyvinyl chloride resin layer are bonded to each other by a method such as wet lamination, dry lamination, or hot melt lamination using the above-mentioned adhesive to form a multilayer structure. It can be. Further, a method such as a so-called calendering method or extruding laminating, in which a polyvinyl chloride resin is extruded into the fiber structure layer to which the above-mentioned adhesive has been applied in advance, can be applied. Further, a method of forming a fibrous structure layer immediately after applying an adhesive to a pre-formed vinyl chloride resin layer is preferably used.

The layer of the polyvinyl chloride resin is (A), the layer of the fibrous structure is (B), and a resin mainly composed of a polymer containing a structural unit represented by the following formula (I) as a bifunctional alcohol component in the molecule. A certain intermediate layer is represented by (C) —OCH ₂ CH (CH ₃ ) (CH ₂ ) ₆ O— (I) and the multilayer body of the present invention is represented by (A) / (C) / (B).

However, when the layer of the same type or another type as (A) or (B) is (D), and the layer made of the same type or other type of adhesive as (C) is (E), the effect of the present invention is obtained. Within a range not impaired, for example, (D) / (E) / (A) / (C) / (B), (D) / (E) / (A) / (C) / (B) / (E) /
(D), (A) / (C) / (B) / (E) / (D), or (D) a multilayer structure may be used.

The multilayer body obtained by laminating the layer of the polyvinyl chloride resin of the present invention thus obtained and the layer of the fibrous structure via an adhesive layer has a soft feeling, and is extremely excellent. It is excellent in normal adhesive strength, low-temperature resistance, and durability (water resistance, heat resistance, flex resistance, etc.), and is extremely useful in practical use, such as shoes, bags and other bags, and clothing.

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

(Production of polyester diol) According to the monomer composition shown in Table I, heating and esterification under a nitrogen stream in accordance with a conventional method using tetripropoxytitanate as a catalyst, followed by a polycondensation reaction under reduced pressure, are described in Table I. Various polyester diols were obtained. The resulting polyester diol was measured for acid value and hydroxyl value according to JIS K0070, and the number average molecular weight was determined.

(Production of Polyester Polyurethane) Using the polyester diol shown in Table I, and using ethyl acetate as a solvent according to the composition shown in Table II, urethanizing the mixture under reflux of the solvent until the conversion of diisocyanate becomes 99.9% or more. The reaction went. Then, ethyl acetate was added to obtain a polyester polyurethane solution having a solid content of 30% by weight.

Examples 1 to 3 and Comparative Examples 1 to 5 The polyester polyurethane solution prepared as described above was used as a main component, and a predetermined amount of a polyfunctional polyisocyanate (Coronate L: manufactured by Nippon Polyurethane Co., Ltd.) was mixed as a curing agent to form an adhesive. Using the adhesive, the following was used as an adherend, and a laminate was obtained in accordance with the combination in Table II.

PVC-1: Dibutyl phthalate (DBP) resin as plasticizer
A flexible polyvinyl chloride sheet containing 70 parts by weight per 100 parts by weight PVC-2: A soft poly (vinyl chloride) sheet containing 90 parts by weight of dioctyl phthalate as a plasticizer and 2 parts by weight of an organotin compound as a stabilizer per 100 parts by weight of resin. Polyvinyl chloride sheet Nylon lid: Nylon taffeta with raw yarn (75 denier / 24 filament) and weft (70 denier / 24 filament), woven density of warp (108 / inch) and weft (82 / inch) PSE taffeta : Yarn is warp (50 denier / 18 filament)
And weft (75 denier / 36 filament), and weaving density is warp (107 yarns / inch) and weft (80 yarns / inch).
Polyester taffeta cotton fabric: The original yarn is warp (20th count) and weft (20th count), and the woven density is warp (65 yarns / inch) and weft (60 yarns / inch) cotton fabric. In Comparative Examples 1 to 4, a predetermined adhesive of a PVC sheet (PVC-1) was applied in an amount of 10 g / m ² after drying, the solvent was evaporated at 45 ° C., and then the fiber structure was heated at a roll temperature of 130 ° C. (Taffeta) was laminated to obtain a laminate. In Example 3 and Comparative Example 5, a predetermined adhesive was applied to a fibrous structure (cotton cloth) in an amount of 10 g / m ² after drying, the solvent was volatilized at 45 ° C., and then preheated at 160 ° C. A laminate was obtained by thermocompression bonding to a PVC sheet (PVC-2) at 160 ° C., 5 kg / cm ² for 60 seconds.

The adhesive strength, hand and durability of the obtained laminate are 40 ° C
After curing for 7 days, the measurement was carried out by the following method, and the results are shown in Table II.

Adhesive strength: 180 ° peel strength was measured under conditions of 20 ° C and 65% relative humidity.

Hand: Judgment of the specimen of the laminate by tactile sensation Durability: 180 ° peeling strength after standing for 2 weeks under conditions of 70 ° C. and 95% relative humidity.

As is clear from Table II, it is clear that the multilayer body of the present invention has good adhesive strength, hand and durability, and high commercial value.

(Effects of the Invention) As described above, according to the present invention, there is provided a laminate of polyvinyl chloride and a fibrous structure, which has a good feeling and a good normal state adhesive strength and durability.

Claims (4)

(57) [Claims] 1. A multilayer body comprising a layer of a polyvinyl chloride resin and a layer of a fibrous structure, wherein a polymer containing a structural unit represented by the following formula (I) as a bifunctional alcohol component in a molecule as an intermediate layer: A multilayer body characterized by interposing a resin mainly composed of: −OCH ₂ CH (CH ₃ ) (CH ₂ ) ₆ O− (I) 2. The bifunctional alcohol component contains structural units represented by the following formulas (I) and (II), and (I) / (I
The multilayer body according to claim 1, wherein I) = 10/90 to 90/10. _{-OCH 2 CH (CH 3) (} CH 2) 6 O- (I) -O (CH 2) 9 O- (II) 3. The multilayer body according to claim 1, wherein the polymer is a polyester polyurethane polyol. 4. The multilayer body according to claim 3, wherein the intermediate layer comprises a polymer which is a polyester polyurethane polyol and a polyfunctional polyisocyanate.