JPS5926471B2 - laminate - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel laminate.

More specifically, the present invention relates to a polyester laminate having excellent heat resistance and chemical resistance, as well as excellent tensile strength and Young's modulus. Conventionally, polyethylene terephthalate film has excellent mechanical strength, heat resistance, and chemical resistance, and has been widely used for fibers, films, and the like.

However, the film (original film) obtained by the melt extrusion method has low strength and Young's modulus, and the reality is that it is usually subjected to stretching treatment for practical use. is difficult to obtain. Furthermore, even if the film is stretched, there are problems in using it in applications that require high strength. Therefore, there is a desire for films and sheets with excellent mechanical and thermal performance. In view of the current situation, the present inventors have arrived at the present invention as a result of intensive studies to obtain a film/sheet that does not require stretching and has excellent mechanical strength.

That is, the present invention provides a laminate in which two or more resin films are bonded together, in which at least two of the resin films are polyester films A that form an anisotropic melt obtained by a melt extrusion method, Moreover, the film A is a laminate characterized in that at least two sheets of the film A are laminated so that their extrusion directions cross each other by 3 (f' or more).

A polyester that forms an anisotropic melt according to the present invention refers to a polyester that transmits polarized light when used in an optical system that includes a differential polarizer.

Preferred examples of such polyesters include aromatic oxycarboxylic acid residues (1), aromatic dicarboxylic acid residues (4), aromatic dihydroxy compound residues mainly containing hydroquinone (), and carbonic acid residues (). Polyester B can be mentioned, and the ratio of the residues (1), (), (), and () satisfies the formula.

The aromatic oxycarboxylic acid residue (1) constituting the polyester B is p-oxybenzoic acid and/or its nuclear substituted derivatives (for example, halogen atoms such as chlorine, bromine, iodine, etc.; methyl, ethyl The main targets are residues of p-oxybenzoic acid derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as a lower alkyl group such as; an alkoxy group such as methoxy, ethoxy, etc. However, some or all of them can be directly replaced with residues of other aromatic oxycarboxylic acids and/or nuclear substituted derivatives thereof. Specific examples of the p-oxybenzoic acid and its nuclear substituted derivatives include p-oxybenzoic acid, 3-
Chlor-4-oxybenzoic acid, 3-bromo-4-oxybenzoic acid, 3-methyl-4-oxybenzoic acid, 3-methoxy-4-oxybenzoic acid, 3.5-dichloro-4-oxybenzoic acid, Examples include 3,5-dibromo-4-oxybenzoic acid.

Among these, p-oxybenzoic acid is particularly preferred. Furthermore, it is particularly preferable that the residue of p-oxybenzoic acid is contained in the residue (1) in an amount of 50 mol% or more. Specific examples of the other aromatic oxybenzoic acids and their nuclear substituted derivatives include m-oxybenzoic acid, 4-chloro-3-oxybenzoic acid, 4-bromo-3-oxybenzoic acid, 5-bromo-3
-oxybenzoic acid, 5-methyl-3-oxybenzoic acid,
Examples include oxynaphthoic acid, oxydiphenylcarboxylic acid, chromium oxynaphthoic acid, and promoxynaphthoic acid. Aromatic oxycarboxylic acids are also
A part of it (for example, 50 mol% or less, preferably 30 mol% or less) may be replaced with an aliphatic oxycarboxylic acid such as ε-oxycaproic acid or an alicyclic oxycarboxylic acid such as cyclohexaneoxycarboxylic acid. can.

Examples of compounds that provide such aromatic oxycarboxylic acid residues (1) include p~oxybenzoic acid residues:
In addition to p-oxybenzoic acid, lower aliphatic carboxylic acid esters such as p-acetoxybenzoic acid, aryl esters such as phenyl p-oxybenzoate, lower alkyl esters such as methyl p-oxybenzoate, p-oxybenzoic acid Examples include acids such as chloride, chlorides, and the like.

Furthermore, examples of aromatic dicarboxylic acid residues include residues such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, methyl terephthalic acid, methyl isophthalic acid, and diphenoxyethane dicarboxylic acid. be able to.

Among these, terephthalic acid residues and isophthalic acid residues are particularly preferred. Residues of such aromatic dicarboxylic acids (4
) can include, in addition to free dicarboxylic acids, their alkyl esters, aryl esters, acid halides, and the like.

In addition, in the present invention, a part (for example, 50 mol% or less, preferably 30 mol% or less) of the aromatic dicarboxylic acid residue (g)
It may be replaced with a residue of other dicarboxylic acids such as aliphatic dicarboxylic acids such as citric acid, adipic acid, sebacic acid, etc.; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Furthermore, the aromatic dihydroxy compound forming the residue () in the polyester BVC is as follows:
It is a compound in which two hydroxyl groups are directly bonded to an aromatic nucleus, and mono-hydroquinone and/or its nuclear-substituted derivatives (e.g. halogen atoms such as chlorine, bromine, iodine, etc.; methyl, ethyl, etc.) The main target is lower alkyl groups (hydroquinone derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as an alkoxy group such as methoxy, ethoxy, etc.), but a portion thereof (for example, 50 mol% Below, preferably 30 mol%
(the following proportions) may be replaced by other aromatic dihydroxy compounds, their nuclear substituted derivatives and/or diols.

Specific examples of hydroquinone and its nuclear-substituted derivatives include hydroquinone, hydroquinone chloride, hydroquinone bromide, hydroquinone iodide, methylhydroquinone, methoxyhydroquinone, and the like. Further, specific examples of other aromatic dihydroxy compounds and their nuclear substituted derivatives include resorcinol, dioxynaphthalene, dioxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis( Examples include 4-hydroxyphenyno(ha)cyclohexane, resorcinol chloride, resorcinol bromide, resorcinol iodide, methylresorcinol, methoxyresorcinol, dioxynaphthalene bromide, etc. Also, as the diol, ethylene glycol, Examples include aliphatic diols such as neopentylene glycol; alicyclic diols such as cyclohexane dimethylol, cyclohexane diol, etc. These may be used alone or in combination of two or more,
Examples of compounds that provide the aromatic dihydroxy compound residue (11) include hydroquinone, such as p-
Examples include esters of aliphatic or aromatic carboxylic acids such as diacetoxybenzene and p-dibenzoyloxybenzene, or carbonate compounds with aromatic hydroxy compounds. Furthermore, examples of compounds that provide carbonic acid residues () constituting polyester B include diaryl carbonates such as diphenyl carbonate, halides such as phosgene, and the like.

The proportions of the aromatic oxycarboxylic acid residue (1), the aromatic dicarboxylic acid residue (), the aromatic dihydroxy compound residue (), and the carbonic acid residue () constituting the polyester B are the respective molar ratios. Letting the numbers be MI, M, M, M, the following formula is satisfied.

More preferably.

Moreover, M is O or a smaller number of moles than M. Furthermore, it is preferable that MI is contained in the polymer in an amount of 10 mol% or more. Such polyester B can be manufactured by a conventional polyester manufacturing method.

For example, p-oxybenzoic acid residue ({) → ( 》-CO-
), terephthalic acid (-0ε×()←Bemaro, hard quinone residue←{卜(?=ra1) and carbonic acid residue (-ha1)
(1) p-oxybenzoic acid and/or phenyl p-oxybenzoate and/or p-
A method of reacting acetoxybenzoic acid, hydroquinone and/or diacetoxybenzene, terephthalic acid and/or diphenyl terephthalate, and diphenyl carbonate in a melt reaction (further solid phase reaction if necessary) or in an inert solvent, (2) p- A method of reacting oxybenzoic acid chloride, hydroquinone, terephthalic acid dichloride, and phosgene in an alkaline solution.

Manufactured by etc.

In the present invention, polyesters forming an anisotropic melt include, in addition to the polyester B, polyesters consisting of residues of hydroquinone nuclear-substituted derivatives and residues of aromatic dicarboxylic acids, such as chlorohydroquinone residues and terephthalate. Acid residues and diphenoxyethane-4,4'
-Dicarboxylic acid residue (molar ratio 80:20 to 70:30)
A copolyester consisting of a chlorohydroquinone residue or a methylhydroquinone residue, a terephthalic acid residue, and a naphthalene-2,6-dicarboxylic acid residue (molar ratio: 70:
30), a copolyester consisting of chlorohydroquinone residue and 4,45-dioxydiphenyl ether residue (molar ratio 90:10) and diphenyl ether -4,4'-
Copolyesters made of dicarboxylic acid residues, copolyesters of polyethylene terephthalate and hydroquinone, polyesters made of p-oxybenzoic acid residues, aromatic dicarboxylic acid residues, and hydroquinone residues, such as p-oxybenzoic acid residues. Copolyester consisting of acid residue, isophthalic acid residue and hydroquinone residue (molar ratio 60:40:40), p-oxybenzoic acid residue, isophthalic acid residue and 4,42-dioxydiphenyl residue ( Copolyesters having a molar ratio of 75:25:25 (Japanese Patent Application Laid-open No. 158695/1982, Japanese Patent Application Laid-open No. 43223/1983, U.S. Patent No. 3804805)
(see specification).

In the present invention, the polyester preferably has an intrinsic viscosity of 0.3 or more, more preferably 0.5 or more, particularly 0.8 or more.

Here, the intrinsic viscosity is 2,4,6-trichlorophenol/
This is a value measured at 35°C in a 50/50 (weight ratio) mixed solvent of 2,4,5-trichlorophenol. The polyester may also contain various additives such as ultraviolet absorbers, heat stabilizers, pigments, and nucleating agents. In the present invention, a film A obtained by melt-extruding the polyester forming the anisotropic melt is used.

The temperature of the film A is, for example, 200 to 400°C, preferably 2
It is obtained by melting it at about 30 to 380°C and extruding it through a T-die with drafts 1 to 10, more preferably 1 to 5. The film A obtained in this way is oriented in the extrusion force direction, and the strength and Young's modulus in that direction are the polyethylene tele J obtained by film forming, stretching and heat treatment.
The film A forming the laminate of the present invention has a tensile strength of 30 kg/Mm2 or more in the extrusion direction, and a tensile strength of 700 kg/1
It is preferable that the material has a Young's modulus of tm2 or more. The film A used in the present invention may be as-melted and extruded, but it is possible to further increase the strength, Young's modulus, and heat resistance by stretching it by several percent and/or heat treatment. The preferred conditions for heat treatment are 200-3
The temperature is 80° C. and the pressure is between normal pressure and reduced pressure. In the laminate of the present invention, at least two of the films constituting the film A are made of the polyester film A that forms the anisotropic melt, and at least two of the films are extruded in directions 3♂ or more from each other. It is necessary that they be laminated in a crossed manner.

The polyester film A forming an anisotropic melt is
Because it is oriented in the extrusion direction, it has extremely excellent performance in the extrusion direction, but it is somewhat inferior in the perpendicular direction. It is necessary to intersect and strike a balance.

Preferably, the number of intersections is 45 or more, more preferably 600 or more. The laminate of the present invention may be formed only from the polyester film A, but may also be laminated together with other resin films.

Examples of such resin films include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, and polytetramethylene-2,6-naphthalene dicarboxylate. polyester such as ester, polyamide such as nylon 6, nylon 66, polyethylene,
Examples include films made of polyolefins such as polypropylene. These may be left unstretched or may be stretched and/or heat treated. The thickness of the film constituting the laminate of the present invention is about 1 to 1000 microns, preferably about 5 to 500 microns. The laminate is produced by adhering and laminating two or more films by a conventionally known method, such as a method of bonding by heat, a method of bonding by ultrasonic waves, a method of bonding by corona discharge, a method of bonding by using an adhesive, etc. can get.

In the case of methods other than using adhesives, the temperature at the time of adhesion is around the flow temperature of the polyester film, preferably in the range of the flow temperature or 10°C lower than the flow temperature, and the adhesion is 5k9/ This can be carried out by applying a pressure of C7l or lower, for example a pressure of about 1 kg/~. Further, when using the resin film as the adhesive layer, the same pressure as described above can be applied at a temperature close to the flow temperature of the film for adhesion. The laminate obtained by the present invention has excellent mechanical performance that is well-balanced vertically and horizontally, and has excellent heat resistance and chemical resistance. , coating materials, etc. The present invention will be explained below with reference to Examples.

Note that "parts" in the examples mean parts by weight. Example 1 96.7 parts of p-oxybenzoic acid, 49.8 parts of isophthalic acid
2 parts, 38.5 parts of hydroquinone and 342.4 parts of diphenyl carbonate in the presence of 0.12 parts of stannous acetate.
The reaction was carried out at a temperature of 50 to 280°C and a pressure of 760 to 0.3 mmH9 to obtain a polymer having an intrinsic viscosity of 179.

The composition of this polymer is p-oxybenzoic acid residue A1...
Idoquinone residue B1 isophthalic acid residue C and carbonic acid residue D are A:B:C:D-50:25:21:4 (molar ratio)
It was hot. Next, after pulverizing and drying this polymer, a Luder type film molding machine was used to reduce the cylinder temperature to 33°C.
It was extruded from a T-die at 0°C onto a rotating drum heated to 150°C. The obtained film was heat treated at 250° C. for 3 hours under reduced pressure of 0.02 H9. The thickness of this film is 48μ, and the tensile strength in the extrusion direction is 56.2k9/Mm.
2. Young's modulus was 2072.8k9/Mm2. The sheets of film were stacked so that the extrusion direction was perpendicular to each other, and placed under a pressure of 5k9/C7i at 290'C for 2 minutes to bond them together.

The thickness of the obtained laminated film was 93μ, and the tensile strength was 37.
．． 0k9/Mm2, Young's modulus is 1323.4k9/Mm
It was 2. In addition, the laminated film was heated at 250°C in a nitrogen stream.
Although it was held for 24 hours, no heat shrinkage was observed.
Example 2 96.6 parts of p-oxybenzoic acid, 33 parts of hydroquinone.
0 parts and 256.8 parts of diphenyl carbonate in the presence of 0.12 parts of stannous acetate at a temperature of 260 to 320°C,
The reaction was carried out under a pressure of 760-0.3 mmHg to obtain a polymer with an intrinsic viscosity of 1.29.

The composition of this polymer is p-oxybenzoic acid residue A1...
Idoquinone residue B and carbonate residue D are A:B:D54:
The molar ratio was 23:23. Next, the polymer was pulverized and dried, and then extruded from a T-die onto a drum heated to 150°C using a Luder type film molding machine at a cylinder temperature of 340°C.

The thickness of the obtained film was 141μ, and the tensile strength in the extrusion direction was 40.8K9. /InJ Young's modulus is 781.7
It was k9/Mm2. This film will be referred to as film A. Separately, a copolymerized polyester produced from terephthalic acid, co-citric acid, and ethylene glycol (terephthalic acid residue E, succinic acid residue F, and ethylene glycol residue H are E:F:H=7:3:10 ( A film (thickness: 53 μm) with a molar ratio of 53 μm was used as film B.

Layer the above film A and film B in the order of film A, film B, film A, and press them for 4 minutes at a temperature of 170°C under a pressure of 5k9/~ so that the extrusion directions of the upper and lower films A are at right angles. and glued it.

The thickness of the obtained laminated film was 293μ, and the tensile strength was 2.
2.6k9/1tm2, Young's modulus is 502.4kg/!
It was Tm2.

Example 3 82.8 parts of p-oxybenzoic acid, 66.4 parts of isophthalic acid
44.9 parts of hydroquinone and Jif-C'.

299.6 parts of carbonate in the presence of 0.06 part of stannous acetate at a temperature of 250-320'C, 760-0.3 m
The reaction was carried out under a pressure of mH9 to obtain a polymer with an intrinsic viscosity of 1.50. The composition of this polymer was p-oxybenzoic acid residue A1...hydroquinone residue B and isophthalic acid residue C in a molar ratio of A:B:C-60:40:40.

Next, after pulverizing and drying this polymer, it was T-shaped at a cylinder temperature of 360°C using a Luder type film forming machine.
It was extruded from a die onto a rotating drum heated to 150°C at a draft rate of 3.

The thickness of the obtained film was 75μ, the tensile strength in the extrusion direction was 31.5kg/7Itm2, and the Young's modulus was 800k9.
/Mm2.

These films were stacked so that the extrusion direction was perpendicular to each other, and heated to 290°C for 2K1! /c-7Il. under the pressure of 2
Let it sit for a minute and let it adhere.

The thickness of the obtained laminated film was 140μ, and the tensile strength was 1
The weight was 8.5 kg/Mm2, and the Young's modulus was 450k9/Mm2. In addition, this laminated film was heated at 25°C in a nitrogen stream.
Although the film was held for 24 hours, no shrinkage of the laminated film was observed.

Example 4 228.5 parts of chlorohydroquinone diacetate, 116.2 parts of terephthalic acid and 64.8 parts of naphthalene-2,6 dicarboxylic acid were mixed at a temperature of 300-350°C, 760-
Reacted under a pressure of 10 mmH9, resulting in an intrinsic viscosity of 2.

Polymer No. 01 was obtained.

The composition of this polymer was terephthalic acid residue A, naphthalene 2,6-dicarboxylic acid residue B, and chlorohydroquinone residue C in a ratio of A:B:C=70:30:100 (molar ratio). Next, after pulverizing this polymer, it was heated to T at a cylinder temperature of 330°C using a Luder type film forming machine.
- It was extruded from a die onto a rotating drum heated to 150°C.

Claims (1)

[Claims] 1. In a laminate in which two or more resin films are bonded, at least two of the resin films are polyester films A that form an anisotropic melt obtained by melt extrusion.
A laminate, characterized in that at least two of the films A are laminated with their extrusion directions crossing each other by 30 or more degrees. 2 Polyester film A forming an anisotropic melt
2. The laminate according to claim 1, wherein at least two sheets of the laminate are joined directly or via another resin film. 3 Polyester film A forming an anisotropic melt
However, residues of aromatic oxycarboxylic acids (I), residues of aromatic dicarboxylic acids (II), residues of aromatic dihydroxy compounds mainly containing hydroquinone (III), and carbonic acid residues (
IV), and the ratio of the residues (I), (II), (III) and (IV) is the formula 30/70≦(M_I +M_II)
/(M_III-M_II)≦99/1, (2/3)・(M
＿III−M_II)＜M_IV≦(3/2)・(M_IIIM_
II), where M_I, M_II, M_III, and M_IV are the number of moles of the above residues (I), (II), (III), and (IV), respectively. Note that M_II is 0 or a smaller number of moles than M_III.
The laminate according to claim 1 or 2, which is a polyester film that satisfies the following.