JPS63203334A - Laminate for sail - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminate used in windsurfing, sailing, etc.

[Prior Art] As a laminate for sails, a laminate in which a fabric is adhered to a polyester biaxially stretched film via an adhesive layer is known. For example, laminates for sails in which fabrics are laminated via an adhesive layer of thermoplastic polyester ether copolymer,
8-222847).

[Problems to be Solved by the Invention] However, the conventional sail laminate has the following problems.

(1) Although the initial adhesive strength between the film and the fabric is within the practical range, the adhesive strength after the kneading test is very small and the bending resistance is poor.

(2) When a sail made using this sail laminate is used, the fabric will peel off from the adhesive layer in the creases of the sail, leech areas and rough areas where high tension is applied to the sail in a short period of time, resulting in poor adhesive durability. There is no.

In order to improve these problems and provide a sail laminate with excellent bending resistance and adhesive durability, the present invention was achieved by conducting detailed studies on the adhesion between films and fabrics and the phenomenon of their peeling. This is what I did.

[Means for Solving the Problems] The present invention provides an adhesive bond between a polyester biaxially stretched film (A) having a thickness of 10 to 100 μm and a fabric (B) having a basis weight of 10 to 500 g/TlI2. Agent layer (C)
A laminate bonded via a bonding force (S1) between the fabric (B) and the adhesive layer (C) and the film (A)
The ratio of the adhesive force (S2) to the adhesive layer (C) is (S1
/S2)>1.1.

The polyester biaxially stretched film (A) in the present invention refers to a biaxially stretched film made by biaxially stretching polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate, polybutylene terephthalate, etc., or a copolymer thereof. film (hereinafter abbreviated as BO film). Particularly preferred is a BO film made of a PET homopolymer or a copolymer containing 90 mol% or more of the PET component. The thickness must be between 10 and 100 μm. When the thickness is less than 10 μm, the elongation of the laminate increases, whereas when the thickness exceeds 100 μm, the laminate becomes hard and difficult to handle. Also, the sail has creases,
Flexibility and adhesive durability decrease.

In this invention, the adhesive layer (C) is made of a well-known adhesive for bonding a polyester-BO film and a fabric, and a thermoplastic resin adhesive or a thermosetting resin adhesive can be used. .

Specifically, copolyester-based, polyester ether-based, acrylic acid-based, methacrylic acid-based, urethane-based,
Adhesives include epoxy, polyamide, and glycidyl methacrylate copolymer adhesives.

Particularly preferred examples are copolyester adhesives and urethane adhesives. As the dicarboxylic acid forming the copolymerized polyester of the copolymerized polyester resin adhesive, in addition to terephthalic acid and isophthalic acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid, dodecanedicarboxylic acid, and the like can be used. Further, as the diol, in addition to ethylene glycol and tetramethylene glycol, trimethylene glycol, neopentyl glycol, hexamethylene glycol, cyclohexane dimetatool, etc. can be used.

The dicarboxylic acid is preferably a copolymer in which 5 to 80 mol%, preferably 10 to 70 mol%, and more preferably 20 to 65 mol% of the dicarboxylic acid is terephthalic acid. Further, the melting point of this copolymer is 40 to 200°C, preferably 80 to 200°C.
The temperature is 180°C, more preferably 100 to 150°C. A blend of copolymerized polyester and polyolefin can also be used.

Urethane adhesives include (1) polyisocyanate adhesives, (2) polyurethane prepolymer adhesives, and (3) polyisocyanate adhesives.
) Isocyanate modified polymer adhesives can be used.

As (1), an adhesive prepared by reacting a known polyisocyanate (for example, "Coronate" L, HL manufactured by Nippon Polyurethane Co., Ltd.) with an active hydrogen-containing material such as polyester, polyether, or polyamine can be used. In (2), a diisocyanate and a polyfunctional active hydrogen compound are reacted to produce a prepolymer with NCO terminals, which is then made into an adhesive using moisture in the air and a curing agent. (3) is a polymer having -0H terminals by reacting a bifunctional or more functional polyester or polyether with a diisocyanate such as tolylene diisocyanate, which is used alone or in combination with a curing agent.

The thickness of the adhesive layer is 10 to 75 μm, preferably 15 to 5 μm.
It is 0 μm, more preferably 20 to 30 μm. If the thickness of the adhesive layer exceeds 75 μm, the resulting laminate will become hard and difficult to handle, and problems will arise in the sail's bending resistance. Conversely, if the thickness is less than 10 μm, a problem arises in that sufficient adhesive strength cannot be obtained. Further, weather resistant agents, heat resistant agents, coloring agents, etc. may be dispersed or blended into the resin used for the adhesive layer.

The fabric (B) in the present invention is composed of filament yarn or stable yarn of polyester, polyamide, aromatic polyamide, polyolefin, polyacrylonitrile, or the like. In particular, fabrics made of filament yarns of polyester or aromatic polyamide are preferred. The forms of the fabric include woven fabric, knitted fabric, non-woven fabric, scrim, split fabric, and net-like fabric. Fabrics and scrims are particularly preferred. More preferred are plain weaves of polyester fibers and scrims thereof, plain weaves and scrims using aromatic polyamide fibers for either warp or weft yarns and polyester fibers for the other yarn.

The fabric may be one that has been subjected to known treatments such as dyeing, softening treatment, water-repellent treatment, and adhesion-promoting treatment. The basis weight of the fabric is 10-500g/ln", preferably 20-500g/ln"
300g/Tn2 is used. Basis weight is 10g/
If it is less than ln2, a laminated body with sufficient strength cannot be obtained, and the tear strength of the laminated body is so low that the sail tends to tear at creases, so it cannot be used. Also, the basis weight is 50
If it exceeds 'Og/Tn', the sail will be too heavy and difficult to handle.

The sail laminate of the present invention includes polyester biaxially stretched film (A)/adhesive layer (C)/fabric (B), and (B)
/(C)/(A)/(C)/(B), (A>/(C)/
(B)/(C)/(A>, etc.), (A) and (
As long as B) is laminated via (C), the number of layers does not matter.

When using plain weave fabric, (A>/(C)/(B)
, or (B)/(C)/(A)/(C)/(B). When using a scrim, (A
)/(C)/(B)/(C)/(A>, etc.) is preferable.

The fabric (B) and the adhesive layer (
The ratio of the adhesive force (S1) with C) and the adhesive force (S2) between the film (A) and the adhesive layer (C) is 81/82>
1.1, preferably S1/S2>1.2. Here, S2 is substantially 1.0 g/25 mm or more, preferably 1.5 kg/25 mm or more. Sl/S2
The upper limit of is actually about 10. S1/S2≦
In the case of 1.1, the bending resistance and adhesive durability are not improved.

Next, typical examples of the method for manufacturing a sail laminate according to the present invention will be described, but the method is not limited thereto.

(1) As an adhesive layer (C) on one side of a polyester-BO film (A>, a copolymerized polyester is melt-extruded laminated or coated with a urethane adhesive solution and then dried in an oven. An adhesive layer is provided. A fabric that has been treated to facilitate adhesion is layered on the adhesive layer (C) side and bonded under heat with a heating roll to form (A)/(C)/(B).
) to obtain a sail laminate having the following configuration.

(2) An adhesive layer (C) with high adhesive strength to the fabric is provided on one side of the polyester-BO film (A), and a fabric (B) that has not been particularly easily bonded is layered and bonded under heat with a heated roll, A sail laminate having the configuration <A>/(C)/(B) is obtained.

(3) The adhesive layer (C) of the above (1) is provided on both sides of the polyester-BO film (A), and the easily bonded fabric (B) is layered on both sides and bonded by thermocompression, or (
Adhesive 1 of the above (2) on both sides of A)! (C) is provided,
A fabric (B) that has not been particularly easily bonded is layered on both sides and bonded by thermocompression (B)/(C)/(A)/(C)/(B).
A sail laminate having the following configuration is obtained.

(4) Lay the (A)/(C) sides of (1) on both sides of the fabric (B) that has been treated with easy adhesion, or on both sides of the fabric (B) that has not been particularly treated with easy adhesion. (2) (A)/(C>) (C) sides are overlapped and thermocompressed (
A sail laminate having a configuration of A>/(C)/(B)/(C)/(A) is obtained.

Adhesive treatment for fabrics refers to treating fabrics with various fiber treatments and resin coatings that have an adhesion effect, such as polyester, epoxy, acrylic, polyamide, silane, rubber, urea, and melamine. It is to process. Further, it is possible to facilitate adhesion using a discharge treatment such as a low temperature plasma treatment (for example, the method described in "Low Temperature Plasma Chemistry", Chemistry Special Issue No. 111, Nankodo).

[Function] When a sail laminate in which a film and a fabric are laminated via an adhesive layer is folded or flapped by the wind, the fibers of the fabric are flexible, so the fibers The amount of deformation at the bonding point between the film and the adhesive layer is larger than the amount of deformation at the bonding point between the film and the adhesive layer (ie, the film interface).

Therefore, bond fatigue is greater in the bond between the fabric and the adhesive layer.

Therefore, if the adhesive force (S1) between the fabric and the adhesive layer is made larger than the adhesive force (S2) between the film and the adhesive layer, the bending resistance and adhesive durability of the laminate can be greatly improved. Ru.

[Method of Measuring Characteristics and Method of Evaluating Effects] The method of measuring characteristic values and the method of evaluating effects of the present invention are as follows.

(1) Flexibility Using an MIT bending tester, a tension of 2 kg is applied to a laminate test piece having a width of 1.5 cm and a length of 11 cm, according to JIS P8115. The number of times it took for the fibers of the fabric to break was used as a measure of bending resistance.

(2) Adhesive Strength Prepare a sample by dipping the end face of the laminate in an organic solvent such as ethyl acetate or chloroform and peeling off the interface between the film and the adhesive layer. Similarly, a sample is made with the interface between the fabric and the adhesive layer peeled off.

These samples were vacuum dried to completely remove the organic solvent.
Make a test piece for adhesion measurement.

The adhesive strength between the fabric and the adhesive layer (S1) and the adhesive strength between the film and the adhesive layer (S2) were measured by the method specified in JIS K 6854-1977. The size of the test piece is 2.5cm wide x 12cm long, and the peeling speed is 20C.
m/min, and the peel angle was 180". (3) Adhesive durability Using a Scotto type tester described in JIS L1096,
A test piece with a width of 2.5 cm and a length of 12 cm was rubbed 100 times.
This is used as a test piece for measuring adhesive strength. The adhesive strength of the rubbed portion of the test piece is measured and defined as 31f (adhesive strength between the fabric and the adhesive layer). If the ratio S1f/S1 to the adhesive strength (S1) of the test piece without rubbing is 80% or more, the adhesive durability is ○, 80
-50% was rated △, and less than 50% was rated ×.

(4) Overall Judgment Items that are excellent as materials for sale are rated ○, and items that have problems in use are rated ×.

[Examples] Example 1 (1) A polyethylene terephthalate film (PET-BO film, "Lumirror" S type manufactured by Toshiku Co., Ltd.) with a thickness of 50 μm was prepared as a polyester BO film.

(2) The fabric is aromatic polyamide fiber (“K” made by DuPont)
A plain weave fabric with the weaving density shown in Table 1 was used, using polyethylene terephthalate fiber (TETRON (strong type 150 denier) manufactured by Toshiku Co., Ltd.) as the weft yarn and using polyethylene terephthalate fiber (TETRON, strong type 150 denier) manufactured by Toshiku Co., Ltd. as the warp yarn. The numerical value of the weave density was as follows.

This fabric was treated to facilitate adhesion using water-soluble epoxy under the following conditions.

The fabric was immersed in water-soluble epoxy ("Bunacol" EX313, Nagase Sangyo Co., Ltd.) and then dried at 180°C. Epoxy adhesion amount 1.5g/ln2゜ (3) As an adhesive,
Urethane adhesive was used.

26% solution of copolyester (MEK/) luene 2
/8) 4.7 parts of "'Coronate" HL (manufactured by Nippon Polyurethane Co., Ltd.) as an incyanate was mixed with 100 parts. The copolymerized polyesters (terephthalic acid/sebacic acid (molar ratio 65/35), ethylene glycol/neopentyl glycol (molar ratio 40/60)) were used.

(4) Manufacturing method of laminate Apply adhesive to PET-BO film using a reverse coater, dry at 80°C in a drying oven, overlap the fabric on the adhesive layer at the exit of the oven, and heat to 150°C. It was crimped with a press roll.

The physical properties of the (A)/(C)/(B) laminate thus obtained were evaluated (Table 1).

Sl/52=1.92, bending resistance ("KevJar'
” was cut after 28,050 times. “Tetron” was not cut)
It had good adhesion durability and was excellent as a laminate for sails.

Example 2 The fabric of Example 1, which had not been treated with epoxy, was treated with low-temperature plasma using argon gas to facilitate adhesion.

The treatment was carried out using a low-temperature plasma device with an internal electrode system, which transports a group of rod-shaped electrodes to which a high voltage was applied and the fabric, and which has a pair of electrodes serving as a ground electrode, under an Ar gas pressure of 0. ITo
The fabric was fabricated at a speed of 7 m/min under the following conditions: RR, high frequency power supply frequency of 110 KHz, negative side output voltage of 4 KV.

A laminate of (A)/(C)/(B) was obtained in the same manner as in Example 1 using this fabric treated to facilitate adhesion. Table 1
As shown in the figure, S1/52=1.88, both the bending resistance and the adhesive durability were good, and the laminate was excellent as a sail laminate.

Comparative Example 1 In addition to using the fabric that was not treated with epoxy in Example 1,
A laminate was produced in the same manner as in Example 1.

As shown in Figure 1, the ratio was as small as 31/52=0.92, so the laminate had poor bending resistance and adhesive durability, making it unsuitable for use as a laminate for sails.

Example 3 (1) The same polyester BO film as in Example 1 was used.

(2) The fabric used was a plain-woven fabric made of "Tetron" having a weave density shown in Table 1 and treated with silane. The processing conditions are as follows. The fabric was immersed in an aqueous solution prepared by hydrolyzing a silane coupling agent (manufactured by Toshi Silicone Co., Ltd., 5H6040) with hydrochloric acid, then squeezed and dried (170° C.).

The amount of silane deposited was 0.159/i2.

(3) A copolymerized polyester adhesive was used as the adhesive. Copolymerized polyester (terephthalic acid/isophthalic acid/adipic acid (molar ratio 56/44)-ethylene glycol/1,4-butanediol (molar ratio 32/68) melting point 112°C) 80 wt% and polyethylene (density 0.923
! l]10+f, MI4.0c+/10m1n) 20
wt% was fed to a melt extrusion laminator with a diameter of 65 mm and a mouthpiece with a width of 1200 mm.
Do not melt at °C. This was melt-extruded between a PET-BO film and a fabric and pressed together with nip rolls. Next, this was passed through a thermocompression roll at 160°C (A)/(C)/
A laminate having the configuration shown in (B) was made. As shown in Table 1, S
1/52 = 1.71, and both the bending resistance (“Tetron” was cut 98,200 times) and adhesive durability are good.
It was an excellent laminate for sails.

Example 4 Example 2 was performed using the non-silanized fabric of Example 3.
In the same way as above, low-temperature plasma treatment was used to facilitate adhesion. <A)/(C)/(B) was prepared in the same manner as in Example 3 using this fabric.
A laminate was obtained. As shown in Table 1, 31/52=1.6
1, which had good bending resistance and adhesive durability, and was excellent as a laminate for sails.

Comparative Example 2 A laminate was produced in the same manner as in Example 3, except that the non-silane-treated fabric of Example 3 was used. As shown in Table 1, S
Since l/52=0.78 was small, both bending resistance and adhesion durability were poor, making it unsuitable for a laminate for sails.

Example 5 (1) “Lumirror” 2 as a polyester BO film
5 μm was prepared.

(2) As the fabric, scrims of 250 denier "Tetron" with 10 threads/inch for both warp and weft threads were used. This scrim was treated with an ethylene urea treatment agent ("0cte").
x″EM (manufactured by Hodogaya Chemical Co., Ltd.).

(3) Using the copolymerized polyester system of Example 3 as an adhesive, melt extrusion was performed on one side of a PET-BO film to a thickness of 15 μm in the same manner as in Example 3, and (A)/(C>
I made a full frame of the composition.

The above scrim is sandwiched between the (C) sides of two facing (A)/(C) films, and the (A)/(C)/(B)/( C)/(A)
I made a laminate with the following structure. 31/52 as shown in Table 1
= 1.80, with good bending resistance and adhesive durability.
It was an excellent laminate for sails.

Comparative Example 3 A laminate was produced in the same manner as in Example 5, except that the scrim that had not been subjected to the adhesive treatment of Example 5 was used. As shown in Table 1, since S1/52=1.0 is small, the bending resistance,
It had poor adhesive durability and was unsuitable for use as a laminate for sails.

[Effects of the invention] The present invention provides polyester BO film (A) and fabric (B).
> is a laminate bonded through an adhesive layer (C), and the ratio of adhesive strength S1 and 82 is S1/S2>1.1, so
It has the following excellent effects.

(1) A sail laminate with excellent bending resistance could be obtained.

(2) Since it was possible to obtain a sail laminate with excellent adhesive durability, peeling of the fabric at the creases, leech portions, and rough portions of the sail could be virtually eliminated.

The thus obtained sail laminate of the present invention is used not only for windsurfing and yacht sails, but also for hang glider wings and the like.

Claims (1)

[Claims] A laminate in which a polyester biaxially stretched film (A) with a thickness of 10 to 100 μm and a fabric (B) with a basis weight of 10 to 500 g/m^2 are adhered via an adhesive layer (C) with a thickness of 10 to 75 μm. the fabric (B) and the adhesive layer (C);
) to the adhesive force (S_2) between the film (A) and the adhesive layer (C) is (S_1/S_
2) A laminate for a sail, characterized in that >1.1.