CN117325532A - 3-layer film for stretching liquid crystal polymer film, stretched 3-layer film, stretched liquid crystal polymer film, and method for producing same - Google Patents
3-layer film for stretching liquid crystal polymer film, stretched 3-layer film, stretched liquid crystal polymer film, and method for producing same Download PDFInfo
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- CN117325532A CN117325532A CN202310755908.2A CN202310755908A CN117325532A CN 117325532 A CN117325532 A CN 117325532A CN 202310755908 A CN202310755908 A CN 202310755908A CN 117325532 A CN117325532 A CN 117325532A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention relates to a 3-layer film for stretching a liquid crystal polymer film, a stretched 3-layer film, a stretched liquid crystal polymer film, and a method for producing the same. Provided is a 3-layer film for stretching a liquid crystal polymer film, which is provided with: a liquid crystal polymer film, and a pair of support films laminated on both sides of the liquid crystal polymer film, at a temperature T 1 Above and at a temperature T 2 At any temperature within the range below, the total value of the yield loads of the pair of support films is larger than the yield load of the liquid crystal polymer film, and the temperature T 1 The glass transition temperature of the liquid crystal polymer constituting the liquid crystal polymer film, the temperature T 2 The melting point of the liquid crystal polymer and the melting point of the polymer constituting the support film are both lower than those of the polymer at-20 ℃.
Description
Technical Field
The present invention relates to a 3-layer film for stretching a liquid crystal polymer film, a stretched 3-layer film, a stretched liquid crystal polymer film, and a method for producing the same.
Background
As a polymer film used for an electronic material, a liquid crystal polymer film excellent in heat resistance, low in water absorption and small in dimensional change rate is known. Since the liquid crystal polymer film is excellent in high frequency characteristics and low dielectric properties, it is expected to be used for flexible printed circuit boards and the like used in the 5 th generation mobile communication system. However, the liquid crystal polymer has a property of easily performing molecular alignment in the flow direction thereof. In a melt extrusion method, which is a general method for producing a film, a liquid crystal polymer of the film produced by the method is molecularly oriented in a longitudinal direction of the film because the polymer is melted and extruded from a T die or the like to form a film, and physical properties such as a dielectric constant and a linear expansion coefficient have anisotropy according to the orientation of the film, so that the film cannot be used for flexible printed circuit boards or the like. In general, the anisotropy of the polymer film is eliminated by stretching in a direction perpendicular to the molecular orientation direction thereof at a temperature lower than the melting point of the film, but the tensile strength of the liquid crystal polymer film extruded from the T die, particularly in the direction perpendicular to the molecular orientation direction, is remarkably low, and therefore, it is easy to break when stretching in the direction perpendicular to the molecular orientation direction is performed at a temperature lower than the melting point of the liquid crystal polymer. As a method for reducing the anisotropy of such a liquid crystal polymer film, the following method is known: a laminate obtained by laminating a thermoplastic resin film on a liquid crystal polymer film is stretched at a temperature equal to or higher than the melting point of the liquid crystal polymer, and after cooling the laminate, the thermoplastic resin film is peeled off to produce a liquid crystal polymer film (for example, patent literature 1). In addition, the following methods are known: a co-extrusion film having a three-layer structure in which an intermediate layer is a liquid crystal polymer layer is formed, and both outer layers are peeled off from the intermediate layer and then stretched (for example, patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 3659721
Patent document 2: international publication No. 2022/124308
Disclosure of Invention
Problems to be solved by the invention
However, in the method of patent document 1, there is a concern that the film surface smoothness is impaired by melting when stretching is performed in a molten state. In the method of patent document 2, although the liquid crystal polymer is stretched at a temperature equal to or lower than the melting point, the stretching ratio is 2 times or lower, and the obtained liquid crystal polymer film cannot eliminate the anisotropy of physical properties.
The purpose of the present invention is to provide: a 3-layer film for stretching a liquid crystal polymer film, which is stretched at a temperature equal to or lower than the melting point, and a method for producing a 3-layer film for stretching a liquid crystal polymer film, which is reduced in anisotropy, can be produced.
Solution for solving the problem
The present inventors have conducted intensive studies on the production of a liquid crystal polymer film reduced in anisotropy, and as a result, found that: according to lamination at temperature T 1 (glass transition temperature of liquid crystal polymer) above and temperature T 2 (either one of the melting point of the liquid crystal polymer and the temperature of-20 ℃ C. Or lower than the melting point of the polymer constituting the supporting film), The above problems can be achieved by a 3-layer film for stretching a liquid crystal polymer film, which has a support film having a yield load in a predetermined range, and the present invention has been completed.
[1]That is, according to the 1 st aspect of the present invention, there is provided a 3-layer film for stretching a liquid crystal polymer film, comprising: a liquid crystal polymer film, and a pair of support films laminated on both sides of the liquid crystal polymer film, at a temperature T 1 Above and at a temperature T 2 At any temperature within the range below, the total value of the yield loads of the pair of support films is larger than the yield load of the liquid crystal polymer film, and the temperature T 1 The glass transition temperature of the liquid crystal polymer constituting the liquid crystal polymer film, the temperature T 2 The melting point of the liquid crystal polymer and the melting point of the polymer constituting the support film are both lower than those of the polymer at-20 ℃.
[2]According to the 2 nd aspect of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to the 1 st aspect, wherein the film is stretched at the temperature T 1 Above and at the aforementioned temperature T 2 At any temperature within the range below, the sum of the maximum point loads of the pair of support films is larger than the maximum point load of the liquid crystal polymer film.
[3]According to aspect 3 of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to aspect 1 or 2, wherein the film is stretched at the aforementioned temperature T 1 Above and at the aforementioned temperature T 2 At least one of the pair of support films has an elongation at break of 200% or more at an arbitrary temperature within the range below.
[4] According to aspect 4 of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 3, wherein the 3-layer film for stretching a liquid crystal polymer film is wound around a cylinder having an outer diameter of 84.2mm so that one of the support films is in contact with the surface thereof, and deformed at a winding angle of 90 ° or more, and further wherein the 3-layer film for stretching a liquid crystal polymer film is wound around the cylinder so that the other one of the support films is in contact with the surface thereof, and is not peeled off between the liquid crystal polymer film and the support film when deformed at a winding angle of 90 ° or more.
[5] According to aspect 5 of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 3, wherein the support film is made of a crystalline resin.
[6] According to aspect 6 of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 5, wherein the support film is composed of aromatic polyether ketone or polyester.
[7] According to aspect 7 of the present invention, there is provided the 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 6, wherein the film thickness of the support film is 5 to 300 μm.
[8] According to aspect 8 of the present invention, there is provided a method for producing a 3-layer film for stretching a liquid crystal polymer film, which is the method for producing a 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 7,
the manufacturing method comprises the following steps: the pair of support films are laminated on both sides of the liquid crystal polymer film according to a pressure lamination method or a heat lamination method.
[9] According to aspect 9 of the present invention, there is provided a method for producing a 3-layer film for stretching a liquid crystal polymer film according to aspect 8, wherein the method for producing a 3-layer film for stretching a liquid crystal polymer film includes the following steps, before the step of laminating the liquid crystal polymer film and the support film: and a step of subjecting both surfaces of the liquid crystal polymer film and a surface of the support film, which is in contact with the liquid crystal polymer film, to surface treatment.
[10] According to aspect 10 of the present invention, there is provided a method for producing a 3-layer film for stretching a liquid crystal polymer film according to aspect 9, wherein the surface treatment is any one of plasma treatment, corona treatment, and chemical conversion treatment.
[11] According to aspect 11 of the present invention, there is provided a method for producing a 3-layer film for stretching a liquid crystal polymer film, which is the method for producing a 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 7, wherein the method for producing a 3-layer film for stretching a liquid crystal polymer film is a melt extrusion method.
[12] According to embodiment 12 of the present invention, there is provided a method for producing a stretched 3-layer film, comprising the steps of: the 3-layer film for stretching a liquid crystal polymer film according to any one of modes 1 to 7 is stretched at least 2.0 to 5.0 times in the TD direction in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
[13] According to aspect 13 of the present invention, there is provided a method for producing a stretched 3-layer film according to aspect 12, wherein after the step of stretching the 3-layer film for stretching a liquid crystal polymer film, the method further comprises the steps of: heat-treating the liquid crystal polymer at a temperature in a range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
[14] According to aspect 14 of the present invention, there is provided a method for producing a stretched liquid crystal polymer film, comprising the steps of: the support film is peeled from the stretched 3-layer film produced by the method for producing a stretched 3-layer film described in any of aspects 12 and 13.
[15] According to embodiment 15 of the present invention, there is provided a method for producing a stretched liquid crystal polymer film, comprising the steps of: a step of peeling the support film from the stretched 3-layer liquid crystal polymer film produced by the method for producing a stretched 3-layer film according to claim 12; and a step of heat-treating the liquid crystal polymer at a temperature in a range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
[16] According to aspect 16 of the present invention, there is provided a stretched 3-layer film obtained by stretching the 3-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 7,
regarding the breaking load measured in 2 directions for the stretched liquid crystal polymer film obtained by peeling the support film, the ratio of the larger breaking load to the smaller breaking load is 6 or less.
[17] According to mode 17 of the present invention, there is provided a stretched liquid crystal polymer film produced by the method for producing a stretched liquid crystal polymer film according to mode 14 or 15,
regarding the breaking load measured in 2 directions for the aforementioned stretched liquid crystal polymer film, the ratio of the larger breaking load to the smaller breaking load is 6 or less.
[18] According to aspect 18 of the present invention, there is provided a stretched liquid crystal polymer film according to aspect 17, wherein the melting point of the stretched liquid crystal polymer film is equal to or higher than the melting point of the liquid crystal polymer film before stretching.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the 3-layer film for stretching a liquid crystal polymer film of the present invention, a stretched liquid crystal polymer film reduced in anisotropy can be produced.
Drawings
Fig. 1 is a schematic view showing a method of evaluating adhesion force between a liquid crystal polymer film and a support film of a 3-layer film for stretching a liquid crystal polymer film in examples, which is a cross-sectional view of a 3-layer film for stretching a liquid crystal polymer film and a 3-inch core.
Fig. 2 is a graph showing the results of a viscoelasticity measurement test of the liquid crystal polymer film used in example 1.
Fig. 3 is a graph showing SS curves according to a tensile test of the liquid crystal polymer film and the support film used in example 4.
Fig. 4 is a graph showing SS curves according to a tensile test of the liquid crystal polymer film and the support film used in comparative example 4.
Description of the reference numerals
10 … liquid Crystal Polymer film 3-layer film for stretching
11. 12 … end portion
21. 22 … support film
30 … liquid Crystal Polymer film
50 … inch core
51 … central axis
Detailed Description
< 3-layer film for stretching liquid Crystal Polymer film >
The 3-layer film for stretching a liquid crystal polymer film of the present invention comprises a liquid crystal polymer film and a pair of support films laminated on both sides of the liquid crystal polymer film. The 3-layer film for stretching a liquid crystal polymer film of the present invention is used for producing a stretched liquid crystal polymer film by peeling a support film from a liquid crystal polymer film after stretching it.
< liquid Crystal Polymer film >
The liquid crystal polymer film used in the present embodiment is a film formed of a liquid crystal polymer. The liquid crystal polymer is not particularly limited, and a liquid crystal polyester showing thermotropic liquid crystal properties is preferable. Examples of such liquid crystal polyesters include aromatic polyesters synthesized from monomers such as aromatic diols, aromatic carboxylic acids, and hydroxycarboxylic acids, which exhibit liquid crystallinity when melted. Specifically, a polycondensate of ethylene terephthalate and parahydroxybenzoic acid, a polycondensate of phenol and phthalic acid and parahydroxybenzoic acid, a polycondensate of hydroxynaphthoic acid and parahydroxybenzoic acid, and the like can be exemplified. In particular, from the viewpoint of excellent mechanical properties, electrical properties, heat resistance, and the like, an aromatic polyester-based liquid crystal polymer having 6-hydroxy-2-naphthoic acid and its derivative as a basic structure and having at least 1 or more selected from the group consisting of p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, 6-naphthalenedicarboxylic acid, 4' -biphenol, bisphenol a, hydroquinone, 4-dihydroxybiphenol, ethylene terephthalate, and its derivative as a monomer component is preferable. The liquid crystal polyester may be used alone in 1 kind, or may be used in 2 or more kinds in any combination and ratio.
The method for synthesizing the liquid crystal polyester is not particularly limited and may be, for example, melt polymerization, melt acidolysis, slurry polymerization, or the like. When these polymerization methods are used, acylation or even acetylation may be performed according to a conventional method.
The liquid crystal polymer may also contain, within a range that does not detract from the effects of the invention: a polymer such as a fluororesin, a polyolefin, a polycycloolefin, a polyetherimide or a silicone modified polyetherimide, a mold release improver such as a higher fatty acid having 10 to 25 carbon atoms, a higher fatty acid ester, a higher fatty acid amide or a higher fatty acid metal salt, a chain extender such as an aliphatic carbodiimide, an alicyclic carbodiimide or an aromatic carbodiimide, a colorant such as a dye, a pigment or carbon black, an organic filler, an inorganic filler, hollow particles, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antirust agent, a foaming agent or an antifoaming agent, or an additive such as a fluorescent agent. These polymers and additives may be contained in the molten resin composition at the time of film formation of the liquid crystal polymer film. In addition, these polymers and additives may be used singly or in combination of 1 or more than 2 kinds. The content of the polymer and the additive is not particularly limited, but is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and still more preferably 0.5 to 30% by mass, based on the total amount of the liquid crystal polymer film, from the viewpoints of moldability, thermal stability, and the like. These polymers, additives, and the like may be added to the liquid crystal polymer in advance, but may be added to the liquid crystal polymer at the time of forming a stretched liquid crystal polymer film described later.
The liquid crystal polymer film can be produced according to a known method. For example, a liquid crystal polymer film can be formed by forming a liquid crystal polymer into a film by a melt extrusion film forming method using a T die (T die melt extrusion). Specifically, a liquid crystal polymer is melt kneaded in an extruder, and the molten resin is extruded through a T die and solidified on a metal roll, whereby a liquid crystal polymer film can be obtained. In the case of curing on a metal roll, contact molding based on rubber rolls or metal rolls may also be used. The barrel temperature of the extruder is preferably 230 to 360 ℃, more preferably 280 to 350 ℃. The slit interval of the T-die may be appropriately set according to the kind and composition of the liquid crystal polymer used, the performance of the target film, and the like. The slit interval of the T die is not particularly limited, but is preferably 0.1 to 1.5mm, more preferably 0.3 to 1.0mm.
The thickness of the liquid crystal polymer film obtained by the above method is not particularly limited, but is preferably 10 to 500. Mu.m, more preferably 20 to 300. Mu.m, still more preferably 30 to 250. Mu.m, from the viewpoints of handleability and productivity at the time of melt extrusion molding by a T die.
The melting point of the liquid crystal polymer constituting the liquid crystal polymer film is preferably 250 to 380 ℃, more preferably 280 to 350 ℃. The glass transition temperature of the liquid crystal polymer constituting the liquid crystal polymer film is preferably 90 to 150 ℃, more preferably 100 to 120 ℃.
< support film >
The support film is a polymer film laminated on the liquid crystal polymer film to prevent the film from being broken when the liquid crystal polymer film is stretched. As the support polymer constituting the support film, crystalline resins are preferably used, and aromatic polyether ketone or polyester, for example, is preferably used. As specific examples of the aromatic polyether ketone, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone (PEKK), polyether ether ketone (PEEKK), and the like can be exemplified. Specific examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and the like. These polymers may be used singly or in combination of 2 or more. Further, these films are preferably crystalline or stretched films in terms of high heat resistance and being stretchable at high temperature. As the polymer used as the support film, as described later, a polymer that satisfies the characteristics of the yield load and the maximum point load and the characteristics of the elongation at break satisfying the predetermined characteristics in comparison with the liquid crystal polymer is preferably selected.
The thickness of the support film is preferably 5 to 300. Mu.m, more preferably 15 to 100. Mu.m.
The support film used in the present invention has the following characteristics. I.e. at temperature T 1 Above and at a temperature T 2 At any temperature in the following range, the total value of the yield loads of the pair of support films becomes larger than the yield load of the liquid crystal polymer film. Here, the temperature T 1 Is the glass transition temperature, temperature T, of the liquid crystal polymer 2 Is the melting point of the liquid crystal polymer, and the melting point of the polymer constituting the support film-any one of temperatures of 20 ℃ (a temperature 20 ℃ lower than the melting point of the polymer constituting the support film). As described later, the 3-layer film for stretching a liquid crystal polymer film of the present invention can be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer film and a stretching ratio of 2 times or higher, whereby a stretched liquid crystal polymer film with small anisotropy can be produced.
It is considered that when a laminate of a liquid crystal polymer film and a support film is stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer, stress concentrates on the liquid crystal polymer film, and breakage occurs. When a tensile test is performed on a liquid crystal polymer film, an SS curve obtained by setting the horizontal axis to an elongation and the vertical axis to a load has a shape in which the load decreases as the elongation increases (see fig. 3). This is considered to be because the portion becomes thin by stretching and the strength is low. Further, it is considered that the tensile stress concentrates on the portion, and the portion is further easily stretched, so that the thickness unevenness of the liquid crystal polymer film cannot be eliminated, and breakage occurs from the thinned portion. In order to avoid such a problem, in the conventional technique for producing a liquid crystal polymer film shown in patent document 1, the liquid crystal polymer is usually stretched at a temperature equal to or higher than the melting point of the liquid crystal polymer in a state where the liquid crystal polymer is molten.
In contrast, the 3-layer film for stretching a liquid crystal polymer film according to the present invention can be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer and a stretching ratio of 2 times or higher by satisfying the above conditions in relation to the yield load of the support film and the yield load of the liquid crystal polymer. The reason why the liquid crystal polymer film can be stretched at a temperature equal to or lower than the melting point by satisfying the above-described relation between the yield load of the liquid crystal polymer film and the yield load of the support film in the present invention is not clear, but is considered as follows. Here, consider the temperature T 2 The melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film by-20 ℃. First, the present invention is carried out at a temperature in the range of from the glass transition temperature of the liquid crystal polymer to the melting point of the liquid crystal polymer (for example, 150 to 280 ℃ C.)The liquid crystal polymer film was stretched by heating the 3-layer film, so that the elastic modulus of the liquid crystal polymer was lower than 1000MPa, and soft portions were produced in the liquid crystal polymer film. In the present invention, the support films are disposed on both sides of the liquid crystal polymer film, and the total value of the yield loads of the pair of support films is higher than the yield load of the liquid crystal polymer film in a temperature range of the glass transition temperature of the liquid crystal polymer or higher and the melting point of the liquid crystal polymer or lower. Thereby, the stretching load applied when stretching the 3-layer film for stretching the liquid crystal polymer film is supported by the support film. Therefore, the liquid crystal polymer film is stretched and thinned, and even if a portion where the load is reduced is generated, the concentration of the tensile stress at the portion where the load is reduced can be suppressed. Further, since the support film is in close contact with the liquid crystal polymer film, the stretching force is uniformly applied to the liquid crystal polymer film through the interface with the liquid crystal polymer film as the support film is stretched. From the above, it is considered that the liquid crystal film can be stretched without breaking. The temperature T 2 It is considered that the liquid crystal film can be stretched without breaking for the same reason even when the melting point of the polymer constituting the support film is at a temperature of-20 ℃, that is, when the melting point of the polymer constituting the support film is at a temperature of-20 ℃ lower than the melting point of the liquid crystal polymer.
The SS curve obtained by the tensile test of the support film used in the present invention has a shape in which the stress increases as the elongation increases (see fig. 3), and the load tends to increase as the support film stretches. Therefore, when stretching a 3-layer film for stretching a liquid crystal polymer film, the load of the thinned portion of the support film increases, and the tensile stress applied to the support film preferentially acts on the thick portion (non-stretched portion) of the support film, so that the entire support film is uniformly stretched. Therefore, in the 3-layer film for stretching a liquid crystal polymer film of the present invention, the support film is adhered to both surfaces of the liquid crystal polymer film, and when the 3-layer film for stretching a liquid crystal polymer film is stretched, the liquid crystal polymer film is uniformly stretched as the support film is uniformly stretched, and therefore, the thickness of the resulting stretched liquid crystal polymer film can be made uniform.
It is preferable that the temperature T be the whole 1 Above and at a temperature T 2 The total value of the yield load of the pair of support films is greater than the yield load of the liquid crystal polymer film over the entire region of the temperature range below. Temperature T 2 In the case of the melting point of the liquid crystal polymer, that is, in the case where the melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film by-20 ℃, for example, the total value of the yield loads of the pair of support films over the entire temperature range of 150 to 280 ℃ is preferably larger than the yield load of the liquid crystal polymer film. In addition, temperature T 2 In the case where the melting point of the polymer constituting the support film is at a temperature of-20 ℃, that is, in the case where the melting point of the polymer constituting the support film is at a temperature of-20 ℃ lower than the melting point of the liquid crystal polymer, for example, the total value of the yield loads of the pair of support films over the entire temperature range of 150 to 260 ℃ is preferably larger than the yield load of the liquid crystal polymer film. However, the temperature T is not always the same 1 Above and at a temperature T 2 The following temperature ranges satisfy the above relationship over the entire area. For example, stretching a 3-layer film of a liquid crystal polymer film at a temperature T 1 Above and at a temperature T 2 When the stretching is performed at a temperature below, the yield load of the liquid crystal polymer film and the support film measured at the specific temperature may satisfy the above-described relationship.
In addition, the support film used in the present invention preferably has the following characteristics. That is, it is preferable that the temperature T 1 Above and at a temperature T 2 At any temperature in the following range, the total value of the maximum point loads of the pair of support films becomes larger than the maximum point load of the liquid crystal polymer film. As described later, the 3-layer film for stretching a liquid crystal polymer film according to the present invention can be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer film, whereby a stretched liquid crystal polymer film having low anisotropy can be produced.
In addition, the support film used in the present invention is preferably: at temperature T 1 Above and at a temperature T 2 In the following temperature range, the elongation at break is 200% or more. It should be noted thatAt least one of the 2 support films laminated on the liquid crystal polymer film may have an elongation at break of 200% or more. As described later, the 3-layer film for stretching a liquid crystal polymer film according to the present invention can be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer film, whereby a stretched liquid crystal polymer film having low anisotropy can be produced.
The yield load, maximum point load, and elongation at break of the support film can be determined as follows: the support film was subjected to a tensile test to obtain an SS curve with the vertical axis being stress and the horizontal axis being elongation, and the SS curve was obtained.
< method for producing 3-layer film for stretching liquid Crystal Polymer film >
The 3-layer film for stretching a liquid crystal polymer film of the present invention can be produced by laminating the liquid crystal polymer film with the 1 st support film and the 2 nd support film according to a pressure lamination method or a thermal lamination method.
In the thermal lamination method, the laminated film of the liquid crystal polymer film and the support film is heated by a pair of heated rolls while the liquid crystal polymer film and the support film are pressure-bonded. The conditions in the thermal lamination method can be appropriately selected depending on the physical properties of the liquid crystal polymer and the supporting polymer. The heating and pressure bonding are preferably performed at a temperature near the melting point of the liquid crystal polymer and a temperature near the melting point of the supporting polymer, without particular limitation.
In the pressure lamination method, a film surface treatment such as plasma treatment is performed on the bonding surface of the liquid crystal polymer and the supporting polymer to improve adhesion, and immediately after the press-down is performed, the liquid crystal polymer film and the supporting film are pressed together. The conditions in the pressure lamination method can be appropriately selected depending on the physical properties of the liquid crystal polymer and the supporting polymer.
In the method for producing a 3-layer film for stretching a liquid crystal polymer film, it is preferable that the surface treatment be performed on the surface (bonding surface) of the liquid crystal polymer film that contacts the support film and the surface (bonding surface) of the support film that contacts the liquid crystal polymer film, respectively, before the step of laminating the liquid crystal polymer film and the 1 st and 2 nd support films. As a method of surface treatment, there can be exemplified: a plasma treatment in which a gas in a plasma state is irradiated to a surface to form electric energy, a corona treatment in which the surface is activated by electric discharge, a method in which ultraviolet rays or electron beams are irradiated to the surface to activate the surface, a method in which flames are brought into contact with the surface to activate the surface, a chemical conversion treatment in which the surface is oxidized by potassium dichromate or the like, a pretreatment agent treatment in which a pretreatment agent is applied, and the like. By performing such surface treatment before bonding the liquid crystal polymer film and the support film, the adhesion between the liquid crystal polymer film and the support film can be improved. The surface treatment method may be appropriately selected depending on the physical properties of the liquid crystal polymer and the supporting polymer, and is preferably plasma treatment, corona treatment, or chemical conversion treatment, particularly preferably plasma treatment, from the viewpoint of improving the adhesion between the liquid crystal polymer film and the supporting film and reducing the damage to the stretched liquid crystal polymer film obtained from the 3-layer film for stretching a liquid crystal polymer film.
As described above, the 3-layer film for stretching a liquid crystal polymer film of the present invention can be obtained.
In the above method, the film made of the liquid crystal polymer and the film made of the supporting polymer are laminated to obtain the 3-layer film for stretching the liquid crystal polymer film, but the method for obtaining the 3-layer film for stretching the liquid crystal polymer film is not particularly limited thereto. For example, a 3-layer film for stretching a liquid crystal polymer film can be formed by a melt extrusion method in which a liquid crystal polymer is melted in an extruder 1 and a support polymer is melted in an extruder 2, and the polymers are extruded into a film shape so that the layers made of the support polymer are laminated on one side or both sides of the layer made of the liquid crystal polymer. The support polymer may be the same as the polymer constituting the support film.
As a method of laminating a layer formed of a supporting polymer on one side or both sides of a layer formed of a liquid crystal polymer, a method of molding a multilayer extruded film from a T die can be used. Specifically, there may be mentioned: a feeding head method in which a molten liquid crystal polymer and a supporting polymer fed from 2 extruders are fed to a feeding head and joined, and then extruded from a T die into a film; the molten liquid crystal polymer and the supporting polymer are supplied to a T die, respectively, and are overlapped into a film and extruded by a Multi-Manifold method or the like. From the viewpoint of improving the smoothness of the resulting stretched liquid crystal polymer film, the Multi-Manifold method is preferably applied in view of the difference in viscosity and flow characteristics between the liquid crystal polymer and the supporting polymer at the time of melting.
< stretched 3-layer film and method for producing stretched liquid Crystal Polymer film >
The stretched 3-layer film and the stretched liquid crystal polymer film of the present invention can be produced according to the following methods.
First, the 3-layer film for stretching a liquid crystal polymer film obtained by the above method is stretched in the width direction (TD direction), thereby obtaining a stretched 3-layer film. Stretching the laminated film in the width direction can reduce the anisotropy of the resulting stretched liquid crystal polymer film. The method of stretching the laminated film is not particularly limited, and a tenter transverse stretching method in which both ends of the laminated film are sandwiched by jigs and heated and stretched is preferable. The stretching ratio and stretching speed are suitably selected so that the stretched shape and physical properties of the film made of the liquid crystal polymer can be brought into desired ranges while the support film is stretched. The stretching ratio is preferably 2 to 5 times. The stretching speed is preferably 1 to 5000%/min, more preferably 50 to 2500%/min. In order to adjust the degree of orientation of the surface after stretching, stretching in the longitudinal direction (MD direction) may be added as necessary.
The temperature at which the stretching of the 3-layer film for stretching a liquid crystal polymer film is performed is preferably set to a temperature T 1 Above and at a temperature T 2 The following temperatures. Temperature T 2 In the case of the melting point of the liquid crystal polymer, that is, in the case where the melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film by-20 ℃, the temperature at the time of stretching is preferably set to a temperature not lower than the glass transition temperature of the liquid crystal polymer film and not higher than the melting point of the liquid crystal polymer film, specifically, preferably set to a temperature in the range of 150 to 280 ℃, more preferably set to a temperature in the range of 170 to 250 ℃. By setting the temperature at which the laminated film is stretched to a temperature equal to or lower than the melting point of the liquid crystal polymer, the smoothness of the stretched liquid crystal polymer film can be improved, and the thickness unevenness, the absence of streaks, and the film forming property can be improved. Further, it is more preferable that the temperature at the time of stretching the laminated film is equal to or higher than the glass transition temperature of the liquid crystal polymer, because the liquid crystal polymer film is easily stretched. In the present invention, as described above, the total value of the yield loads of the pair of support films becomes larger than the yield load of the liquid crystal polymer film at any temperature in the range of the glass transition temperature of the liquid crystal polymer or higher and the melting point of the liquid crystal polymer or lower, whereby the 3-layer film for stretching the liquid crystal polymer film can be stretched at a temperature of the melting point of the liquid crystal polymer or lower.
In addition, temperature T 2 In the case where the temperature of the melting point of the polymer constituting the support film is-20 ℃, that is, the temperature of the melting point of the polymer constituting the support film is lower than the melting point of the liquid crystal polymer, the temperature at the time of stretching is preferably set to a temperature of not lower than the glass transition temperature of the liquid crystal polymer film and not higher than the temperature of the melting point of the polymer constituting the support film, that is, not higher than the melting point of the polymer constituting the support film, specifically, preferably set to a temperature in the range of 150 to 260 ℃, and preferably set to a temperature in the range of 150 to 230 ℃.
Then, the stretched 3-layer film is preferably heat-treated at a temperature in the range of not less than the glass transition temperature and not more than the melting point of the liquid crystal polymer film. The heat treatment is preferably performed for 1 to 100 hours, more preferably 3 to 48 hours. By performing the heat treatment, the heat resistance of the stretched liquid crystal polymer film can be improved, and the linear expansion coefficient can be reduced.
The melting point of the liquid crystal polymer constituting the liquid crystal polymer film in the 3-layer film for stretching a liquid crystal polymer film after stretching and heat treatment is preferably not less than the melting point of the liquid crystal polymer constituting the liquid crystal polymer film before stretching.
Finally, the support films laminated on both sides of the liquid crystal polymer film are peeled off, whereby a stretched liquid crystal polymer film can be obtained. The anisotropy of the stretched liquid crystal polymer film thus produced is effectively reduced. In particular, anisotropy of molecular orientation and anisotropy of mechanical properties are effectively reduced.
In the above method, the support film is peeled after the heat treatment, but the order of the heat treatment and the support film peeling is not particularly limited, and the heat treatment may be performed after the support film is peeled.
The support film of the stretched 3-layer film may also be peeled off immediately before the stretched liquid crystal polymer film is used. The support film may serve as a protective film for preventing scratches during transportation, for example.
The anisotropy of the molecular orientation of the stretched liquid crystal polymer film was determined as follows. First, in the pole measurement by X-ray diffraction, the diffraction intensity of 110 plane was measured while rotating the stretched liquid crystal polymer film in the in-plane direction (β direction) in a state of being inclined by 45 ° (α=45° in Schulz method), and an X-ray diffraction intensity curve was prepared. In this curve, β=0° is set in the longitudinal direction of the film, the integrated intensities of β=45 to 135 °, 135 ° to 225 °, 225 to 315 °, and 315 to 45 ° are obtained, and the sum of the integrated intensity of β=45 to 135 ° and the integrated intensity of β=225 ° to 315 ° is used as the integrated intensity in the longitudinal direction. The sum of the integrated intensity at β=135 to 225 ° and the integrated intensity at β=315 to 45 ° is taken as the integrated intensity in the width direction. In this case, the degree of plane orientation of the molecular orientation of the stretched liquid crystal polymer film is represented by the following formula (1). The degree of plane orientation represented by the following formula (1) is preferably-0.5 or more and 0.5 or less, more preferably-0.3 or more and 0.3 or less, and still more preferably-0.2 or more and 0.2 or less. According to the 3-layer film for stretching a liquid crystal polymer film of the present invention, a stretched liquid crystal polymer film having a degree of plane orientation controlled within the above-mentioned range can be produced.
Plane orientation degree= (integrated intensity in longitudinal direction-integrated intensity in width direction)/(integrated intensity in longitudinal direction+integrated intensity in width direction) (1)
The diffraction intensity of the 110 plane refers to the diffraction intensity of the crystal plane (110 plane) of the liquid crystal polymer. For example, at 73:27 molar ratio the diffraction intensity at 110 face in the liquid crystal polymer obtained by polycondensing 2, 6-hydroxynaphthoic acid with parahydroxybenzoic acid means: the maximum diffraction intensity observed at 2θ=20° when X-ray diffraction is measured in a range of 10 ° to 40 ° in terms of diffraction angle (2θ). The diffraction intensity of the liquid crystal polymer oriented in the longitudinal direction (110 plane) was set as: since β=90° and 270 ° are maximized when β=0° is set in the longitudinal direction of the film, the sum of the integrated intensity of β=45 to 135° and the integrated intensity of β=225 to 315 ° is set as the integrated intensity in the longitudinal direction, and the sum of the integrated intensity of β=135 to 225 ° and the integrated intensity of β=315 to 45 ° is set as the integrated intensity in the width direction. The integrated intensity is obtained from the area where β is represented as the horizontal axis and the diffraction intensity is represented as the vertical axis. The value represented by the above formula (2) indicates that the molecular chain is oriented in the longitudinal direction if it is a positive value, and indicates that it is oriented in the width direction if it is a negative value.
The anisotropy of the mechanical properties of the stretched liquid crystal polymer film was determined as follows. First, a tensile test was performed in the TD direction of the stretched liquid crystal polymer film by a tensile tester. Based on the SS curve obtained from the results of the tensile test, the breaking load in the TD direction was obtained. Then, a tensile test was also performed in the MD direction of the stretched liquid crystal polymer film, and the breaking load in the MD direction was determined based on the SS curve. The anisotropy of the mechanical properties of the stretched liquid crystal polymer film is expressed as a ratio of the breaking load in the MD direction to the breaking load in the TD direction. The ratio of the breaking load is preferably 6 or less, more preferably 3 or less. The lower limit of the ratio of the breaking load is not particularly limited, and is usually 1 or more. According to the 3-layer film for stretching a liquid crystal polymer film of the present invention, a stretched liquid crystal polymer film in which the ratio of the breaking load is controlled within the above-mentioned range can be produced.
The direction of measurement of the breaking load in the anisotropic evaluation of the stretched liquid crystal polymer film is not particularly limited to the TD direction and the MD direction. For example, the breaking load may be obtained by stretching a liquid crystal polymer film by performing a stretching test in 2 different directions, and the ratio of the larger breaking load to the smaller breaking load may be within the above range. In this case, the ratio of the breaking load measured in 2 directions intersecting at right angles at the surface of the stretched liquid crystal polymer film is preferably within the above range.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
< comparison of yield load (upper yield point) of liquid Crystal Polymer film and support film >
Samples having a width (TD) of 120mm and a length (MD) of 25mm were cut out from the liquid crystal polymer film, and a tensile test was performed in a tensile tester (TENSILON A-500, orientec Co., ltd.) at a predetermined tensile temperature and tensile speed in each example and comparative example so that the tensile direction of the sample became TD. From the results of the tensile test, an SS curve was obtained with tensile stress on the vertical axis and elongation on the horizontal axis. From the SS curve, the yield load (upper yield point) of the liquid crystalline polymer film was determined. The tensile test was performed similarly for the support film to determine the yield load. The measurement values of the yield load of the respective films are shown in table 1. Then, the total value of the yield load of 2 support films (the yield load of 1 support film can be obtained as 2 times) and the yield load of the liquid crystal polymer film are compared and evaluated. In examples 4 and 9 in which a 3-layer film for stretching a liquid crystal polymer film was produced by coextrusion, a support film constituting the 3-layer film for stretching a liquid crystal polymer film was peeled from the liquid crystal polymer film as a sample of the support film, and the yield load was determined for the obtained sample. The evaluation results in each example and comparative example are shown in table 2.
And (2) the following steps: total value of yield load of 2 supporting films > yield load of liquid crystal polymer film
X: the total value of the yield load of 2 supporting films is less than or equal to the yield load of the liquid crystal polymer film
< comparison of maximum Point load of liquid Crystal Polymer film and support film >
The maximum point load of the liquid crystal polymer film was determined based on the SS curve obtained from the results of the stretching test performed on the liquid crystal polymer film at the predetermined stretching temperature and stretching speed in each of examples and comparative examples by the above-described method. The maximum point load of the support film was similarly determined. The measured value of the maximum point load of each film is shown in table 1. Then, the total value of the maximum point loads of 2 support films (the maximum point load of 1 support film can be obtained as 2 times) and the maximum point load of the liquid crystal polymer film are compared, and evaluation is performed as follows. The evaluation results in each example and comparative example are shown in table 2.
And (2) the following steps: total value of maximum point load of 2 supporting films > maximum point load of liquid crystal polymer film
X: the total value of the maximum point load of 2 supporting films is less than or equal to the maximum point load of the liquid crystal polymer film
< elongation at break of support film >
The elongation at break of the support film was determined from the SS curve of the support film determined by the above method and evaluated. The measured values of elongation at break of the respective films are shown in table 1.
TABLE 1
< adhesion force of liquid Crystal Polymer film to support film >
The resulting 3-layer film for stretching a liquid crystal polymer film was wound around a 3-inch core (plastic cylinder) having an outer diameter of 84.2mm and deformed to visually confirm the presence or absence of peeling of the liquid crystal polymer film from the support film, and the adhesion force between the liquid crystal polymer film and the support film was evaluated. Specifically, as shown in fig. 1, the 3-layer film 10 for stretching a liquid crystal polymer film is wound around the 3-inch core 50 such that the surface of one support film 21 is in contact with the 3-inch core 50. At this time, when the cross section of the 3-inch core 50 is observed, the angle θ (hereinafter referred to as a winding angle) between the two ends 11 and 12 of the 3-layer film 10 for stretching a liquid crystal polymer film and the central axis 51 of the 3-inch core 50 is set to 90 ° or more. The winding angle θ may be 90 ° or more but is usually 160 ° or less. After the entire surface of the support film 21 was kept in close contact with the 3-inch core 50 for 5 seconds, the 3-layer film 10 for stretching a liquid crystal polymer film was peeled from the 3-inch core 50. Next, the 3-layer film 10 for stretching a liquid crystal polymer film is turned over so that the other support film 22 is in contact with the 3-inch core 50, and is wound around the 3-inch core 50 again. In this case, the winding angle θ is also set to 90 ° or more. After holding for 5 seconds in this state, the 3-layer film for stretching a liquid crystal polymer film 10 was peeled from the 3-inch core 50. After that, the presence or absence of peeling between the liquid crystal polymer film 30 and the support films 21 and 22 of the 3-layer film 10 for stretching a liquid crystal polymer film was confirmed. Fig. 1 is a schematic view showing a method of evaluating adhesion force between a liquid crystal polymer film and a support film of a 3-layer film for stretching a liquid crystal polymer film in examples, which is a cross-sectional view of a 3-layer film for stretching a liquid crystal polymer film and a 3-inch core.
And (2) the following steps: no peeling occurs between the liquid crystal polymer film and the support film, and the adhesion is excellent.
X: peeling occurs between the liquid crystal polymer film and the support film, and the adhesion force is insufficient.
< peelability of support film >
The stretched 3-layer films of examples 1, 2 and 4 to 11 after the heat treatment were peeled off from both the support films laminated on both sides of the stretched liquid crystal polymer film, and the surface state of the stretched liquid crystal polymer film was visually confirmed. The peelability of the support film was evaluated based on the presence or absence of the residue of the support film on the surface of the stretched liquid crystal polymer film. The same evaluation was performed on the stretched 3-layer film of example 3, which was not subjected to heat treatment.
And (2) the following steps: the residue of the supporting film is not contained, and the peeling property of the supporting film is excellent.
X: there is a residue of the support film, and the peelability of the support film is insufficient.
< stretchability of 3-layer film for stretching liquid Crystal Polymer film >
The thickness unevenness, streaks, and the like of the stretched liquid crystal polymer film produced using the 3-layer film for stretching a liquid crystal polymer film were visually evaluated.
And (2) the following steps: has no uneven thickness and no stripes, and is good.
Delta: uneven thickness and streaks are visible.
X: uneven thickness and large cracks.
< degree of plane orientation of stretched liquid Crystal Polymer film >
For the stretched liquid crystal polymer film, the diffraction angle (2θ) was fixed to 20 ° by using a sample-level type multi-purpose X-ray diffraction device (model: ultima IV, manufactured by Rigaku Corporation), and the film was used as an X-ray target: cu, voltage: 40kV and current: the pole measurements were performed at 40mA, α angle=45°, and β angle=0 to 360 ° (the longitudinal direction of the film was set to 0 °, and the step angle was set to 5 °), and an X-ray diffraction intensity curve was produced. When the integrated intensities of β=45 to 135 °, 135 ° to 225 °, 225 to 315 °, and 315 to 45 ° of the curve are obtained, and the sum of the integrated intensities of β=45 to 135 ° and β=225 to 315 ° is taken as the integrated intensity in the longitudinal direction and the sum of the integrated intensities of β=135 to 225 ° and β=315 to 45 ° is taken as the integrated intensity in the width direction, the surface orientation degree is obtained by the following expression (2).
Plane orientation degree= (integrated intensity in longitudinal direction-integrated intensity in width direction)/(integrated intensity in longitudinal direction+integrated intensity in width direction) (2)
< ratio of breaking Strength of stretched liquid Crystal Polymer film >
Samples having a width (TD) of 120mm and a length (MD) of 25mm were cut out from a stretched liquid crystal polymer film produced from a 3-layer film for stretching a liquid crystal polymer film, and the samples were set in a tensile tester so that the stretching direction of the samples became TD, and subjected to a tensile test. The breaking load in TD was determined from the SS curve obtained from the results of the tensile test. Next, a sample of the stretched liquid crystal polymer film was set in a tensile tester so that the stretching direction of the sample became MD, and a tensile test was performed. The breaking load in the MD was determined from the SS curve obtained from the result of the tensile test. Then, the ratio of the breaking load in the MD to the breaking load in the TD was obtained.
< melting Point of stretched liquid Crystal Polymer film >
The liquid crystal polymer film before stretching produced in example 1 was heated from 0℃at 10℃per minute using a differential scanning calorimeter (Perkinelmer Co., ltd., model: DSC 8500) as the melting point of the liquid crystal polymer film before stretching. The melting point of the stretched liquid crystal polymer film produced in each example was defined as the endothermic peak temperature observed when the temperature of the stretched liquid crystal polymer film was raised from 0℃at 10℃per minute. The melting point of the liquid crystal polymer film before stretching was 280 ℃. Melting points of stretched liquid crystal polymer films were carried out for examples 1 to 4 and 6.
< glass transition temperature of liquid Crystal Polymer film >
The peak temperature of the loss tangent tan delta measured by heating the liquid crystal polymer film before stretching, which was prepared in example 1, from 30℃at 5℃per minute was used as the glass transition temperature of the liquid crystal polymer film using a viscoelasticity measuring apparatus (DMA 7100, manufactured by Hitachi Ltd.). The glass transition temperatures of the liquid crystal polymer films used in the examples and comparative examples before stretching were 100 to 105 ℃. Fig. 2 is a graph showing the results of a viscoelasticity measurement test of the liquid crystal polymer film used in example 1.
Example 1 ]
Liquid crystal polymer (liquid crystal polymer) (manufactured by Polyplastics co., ltd., LAPEROS a950 RX) was fed to a twin screw extruder (screw diameter: 32 mm), extruded from a T die (lip length: 350mm, lip gap: about 1mm, die temperature: 300 ℃) at the front end of the extruder into a film shape, and cooled to obtain a Liquid Crystal Polymer (LCP) film having a thickness of 75 μm.
Next, on both sides of a liquid crystal polymer Film and on one side of a polyether ether ketone (PEEK) Film (manufactured by Victrex, APTIV Film 1000-025G, thickness 25 μm, surface roughness Ra=0.14 μm (MD), 0.12 μm (TD), melting point 343 ℃) as a supporting Film, an atmospheric pressure plasma treatment was performed in a direct mode under a gas atmosphere containing oxygen at a power of 1.5kW and a transport speed of 1.0 m/min. Next, the plasma treated surfaces were overlapped, and the PEEK film was thermally bonded to both surfaces of the liquid crystal polymer film using a 1 st roll heated to 305 ℃ and a 2 nd roll heated to 120 ℃ under a nip pressure of 0.2MPa and a transport speed of 0.5 m/min. The liquid crystal polymer film and the PEEK film after thermocompression bonding are closely adhered. Thus, a 3-layer film for stretching a liquid crystal polymer film was obtained.
The 3-layer film for stretching a liquid crystal polymer film thus produced was stretched 3-fold in the width direction (TD) in a transverse stretching machine (in-furnace temperature 320 ℃) of a tenter type at a conveying speed of 15 m/min (stretching speed 2500%/min, stretching temperature up to 250 ℃), to obtain a stretched 3-layer film. The stretching reaching temperature means the temperature of the laminated film at the end of stretching. Thereafter, the stretched 3-layer film was subjected to heat treatment at 260℃for 3 hours in an oven, and the PEEK film was peeled off to obtain a stretched liquid crystal polymer film having a thickness of 25. Mu.m, and the peelability of the support film and the stretchability of the 3-layer film for stretching a liquid crystal polymer film were evaluated. Further, the stretched liquid crystal polymer film was evaluated for the degree of plane orientation, the tensile breaking load ratio, and the melting point. The results are shown in Table 2.
Examples 2, 4, 6 to 8 ]
In the same manner as in example 1, a 3-layer film for stretching a liquid crystal polymer film was obtained. Next, a stretched liquid crystal polymer film was obtained in the same manner as in example 1, except that the temperature in the furnace, the stretching speed, the stretching ratio, and the temperature of the heat treatment at the time of stretching were changed to the values described in table 1, and the same evaluation as in example 1 was performed. The results are shown in Table 2.
Example 3 ]
A stretched liquid crystal polymer film was obtained and evaluated in the same manner as in example 2, except that the heat treatment was not performed. The results are shown in Table 2.
Example 5 ]
Liquid crystal polymer (polymer co., ltd., LAPEROS a950 RX) was fed to a twin screw extruder, and melt kneaded at 300 ℃. Further, a polyether ether ketone (PEEK) polymer (manufactured by Polyplastics-Evonik Corporation, 3300G, melting point 342 ℃) as a supporting polymer was fed to a single-screw extruder, and melt-kneaded at 380 ℃. These molten polymers were fed to a Multi-manifield T die, and layers of supporting polymers were laminated on both sides of a layer of a liquid crystal polymer, extruded (co-extruded), and cooled to produce a 3-layer film for stretching a liquid crystal polymer film having 75 μm liquid crystal polymer layers and 25 μm supporting polymer layers on both sides, respectively, and a total of 125 μm. Using the 3-layer film for stretching a liquid crystal polymer film obtained, a stretched liquid crystal polymer film was obtained in the same manner as in example 1, and evaluated in the same manner as in example 1. The results are shown in Table 2.
Example 9 ]
The same procedure as in example 1 was repeated except that the thickness of the liquid crystal polymer film was changed to 200. Mu.m, and the thickness of the polyether ether ketone film as the supporting film was changed to 50. Mu.m, to obtain a 3-layer film for stretching a liquid crystal polymer film, and to obtain a stretched liquid crystal polymer film.
Example 10 ]
A3-layer film for stretching a liquid crystal polymer film was produced in the same manner as in example 5, except that a liquid crystal polymer layer of 75 μm was used as a supporting polymer, and that the supporting polymer layers on both sides were 25 μm each and a total of 125 μm, using an unstretched polybutylene terephthalate (M-PBT) (manufactured by Mitsubishi Engineering-Plastics Corporation, novadura 5026, melting point 220 ℃). The obtained 3-layer film for stretching a liquid crystal polymer film was subjected to stretching and heat treatment under the conditions shown in table 2, and after peeling the support film, the film was evaluated in the same manner as in example 1. The results are shown in Table 2.
Example 11 ]
A 3-layer Film for stretching a liquid crystal polymer Film was obtained in the same manner as in example 1, except that the thickness of the liquid crystal polymer Film was changed to the thickness shown in table 2, and a biaxially stretched PBT Film (BO-PBT) (KOHJIN Film & Chemicals co., ltd., boblet, thickness 25 μm, melting point 220 ℃) was used as a support Film. Using the 3-layer film for stretching a liquid crystal polymer film obtained, stretching and heat treatment were performed under the conditions described in table 2, and after peeling the support film, the evaluation was performed in the same manner as in example 1.
Comparative example 1 ]
The liquid crystal polymer film before lamination with the support film produced in example 1 was evaluated for the degree of plane orientation and the tensile breaking load ratio. The results are shown in Table 2.
Comparative example 2 ]
A3-layer film was obtained in the same manner as in example 1, except that a film having a thickness of 75 μm was used as the liquid crystal polymer film and a porous PTFE film (50 μm in thickness) was used as the support film. As a result of comparing the yield load and the maximum point load of the liquid crystal polymer film with those of the support film, the total value of the yield load at 150 ℃, 200 ℃ and 250 ℃ of 2 support films was lower than that of the liquid crystal polymer film at the same temperature, respectively. In addition, the total value of the maximum point loads at 150 ℃, 200 ℃, 250 ℃ of the 2 support films was lower than the maximum point load of the liquid crystal polymer film at the same temperature, respectively. The 3-layer film was stretched at a stretching temperature of 250℃at a stretching speed of 2500%/min at a stretching ratio of 3 times, and as a result, cracks were generated in the liquid crystal polymer film, and the 3-layer film could not be stretched.
Comparative example 3 ]
In the same manner as in example 1, a liquid crystal polymer film having a thickness of 200 μm was obtained by extruding a liquid crystal polymer into a film shape by a twin screw extruder. Thereafter, a 3-layer film formed of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in example 1, except that an unstretched polybutylene terephthalate (manufactured by Toyo Steel sheet Co., ltd., E sheet, thickness 50 μm) was used as the support film. As a result of comparing the yield load and the maximum point load of the liquid crystal polymer film with those of the support film, the total value of the yield load at 150℃and 200℃of 2 support films was lower than that of the liquid crystal polymer film at the same temperature, respectively. In addition, the total value of the maximum point loads at 150℃and 200℃of 2 support films was lower than the maximum point load of the liquid crystal polymer film at the same temperature, respectively. The 3-layer film was stretched at a stretching temperature of 250℃at a stretching speed of 2500%/min at a stretching ratio of 3 times, and as a result, cracks were generated in the liquid crystal polymer film, and the 3-layer film could not be stretched.
Comparative example 4 ]
A 3-layer film formed of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in example 1, except that an unstretched polybutylene terephthalate (manufactured by eastern Steel sheet Co., ltd., E sheet, thickness 35 μm) was used as the support film. As a result of comparing the yield load and the maximum point load of the liquid crystal polymer film with those of the support film, the total value of the yield load at 150℃and 200℃of 2 support films was lower than that of the liquid crystal polymer film at the same temperature, respectively. The 3-layer film was stretched at a stretching temperature of 200℃and a stretching speed of 2500%/min at a stretching ratio of 3 times, and as a result, cracks were generated in the liquid crystal polymer film, and the 3-layer film could not be stretched.
Comparative example 5 ]
A 3-layer film formed of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in example 1, except that polymethylpentene (PMP) (thickness 50 μm) was used as the support film. As a result of comparing the yield load and the maximum point load of the liquid crystal polymer film with those of the support film, the total value of the yield load at 150℃and 200℃of 2 support films was lower than that of the liquid crystal polymer film at the same temperature, respectively. In addition, the total value of the maximum point loads at 150℃and 200℃of 2 support films was lower than the maximum point load of the liquid crystal polymer film at the same temperature, respectively. The 3-layer film was stretched at a stretching temperature of 200℃and a stretching speed of 2500%/min at a stretching ratio of 3 times, and as a result, cracks were generated in the liquid crystal polymer film, and the 3-layer film could not be stretched.
Reference example 1 ]
A stretched liquid crystal polymer film was obtained in the same manner as in example 1, except that the stretching ratio was changed to 1.5 times and the heat treatment temperature was changed to 250℃to obtain a 3-layer film for stretching a liquid crystal polymer film. The results are shown in Table 2.
Reference example 2]
A 3-layer film for stretching a liquid crystal polymer film was obtained in the same manner as in example 1, except that the liquid crystal polymer film and the support film were not subjected to surface treatment. The 3-layer film for stretching a liquid crystal polymer film obtained was used, and the stretching was performed under the conditions described in table 2, and as a result, cracks were generated in the liquid crystal polymer film, and the 3-layer film could not be stretched. The results are shown in Table 2.
TABLE 2
Fig. 3 is a graph showing SS curves according to a tensile test of the liquid crystal polymer film and the support film used in example 4. In the graph of fig. 3, the horizontal axis represents elongation (mm) in the tensile test, and the vertical axis represents load (N) applied to the film in the tensile test. The tensile test was performed as follows: samples (length in TD direction: 25mm, length in MD direction: 25 mm) of a liquid crystal polymer film (LCP) and a support film (PEEK) were set in a tensile tester (20 mm between chucks) so that the tensile direction became TD, preheated in a constant temperature bath at 150℃for 5 minutes, and then stretched to 3 times (60 mm in chuck pitch) at a tensile speed of 2500%/minute. In fig. 3, the SS curve of the support film is composed of a value 2 times the load (load of 2 tensors of the support film) measured in the tensile test of the support film. As shown in fig. 3, in the 3-layer film for stretching a liquid crystal polymer film of example 4, the total value of the yield load of the support film at 150 ℃ was higher than that of the liquid crystal polymer film. Similarly, in the 3-layer film for stretching a liquid crystal polymer film obtained in example 1, the total value of the yield load of the support film at 250 ℃ was higher than that of the liquid crystal polymer film. Similarly, in the 3-layer films for stretching of the liquid crystal polymer films obtained in examples 2 and 3, the total value of the yield load of the support film at 275 ℃ was higher than that of the liquid crystal polymer film. From the above, in the 3-layer film for stretching a liquid crystal polymer film using a Polyetheretherketone (PEEK) film as a support film, the total value of the yield load of the support film is higher than that of the liquid crystal polymer film over the entire temperature range of 150 to 275 ℃.
In examples 1 to 11, by using a 3-layer film for stretching a liquid crystal polymer film in which the total value of the yield load of the support film is higher than the yield load of the liquid crystal polymer film in a predetermined temperature range, the liquid crystal polymer film can be stretched at a temperature of 2 times or more of the stretching ratio at a temperature of the melting point of the liquid crystal polymer or less, and a stretched liquid crystal polymer film having a small in-plane orientation degree and fracture load ratio and effectively reduced anisotropy can be obtained.
Fig. 4 is a graph showing SS curves according to a tensile test of the liquid crystal polymer film and the support film used in comparative example 4. In the graph of fig. 4, the horizontal axis represents elongation (mm) in the tensile test, and the vertical axis represents load (N) applied to the film in the tensile test. The tensile test was performed as follows: samples (length in TD direction: 25mm, length in MD direction: 25 mm) of a liquid crystal polymer film (LCP) and a support film (PBT) were set in a tensile tester (20 mm between chucks) so that the tensile direction became TD, preheated in a constant temperature bath at 150℃for 5 minutes, and then stretched to 3 times (60 mm in chuck pitch) at a stretching speed of 2500%/minute. In fig. 4, the SS curve of the support film is composed of a value 2 times the load (load of 2 tensors of the support film) measured in the tensile test of the support film. As shown in fig. 4, in comparative example 4, the total value of the yield load of the support film at 150 ℃ was lower than that of the liquid crystal polymer film. Therefore, in comparative example 4, cracks were generated in the liquid crystal polymer film when the 3-layer film was stretched.
Claims (18)
1. A3-layer film for stretching a liquid crystal polymer film, comprising:
liquid crystal polymer film
A pair of support films laminated on both sides of the liquid crystal polymer film,
at temperature T 1 Above and at a temperature T 2 At any temperature within the range below, the total value of the yield loads of a pair of the support films is greater than the yield load of the liquid crystal polymer film,
said temperature T 1 To form the glass transition temperature of the liquid crystal polymer film,
said temperature T 2 Is either one of the melting point of the liquid crystal polymer and the temperature of-20 ℃ which is the melting point of the polymer constituting the support film.
2. The 3-layer film for stretching a liquid crystal polymer film according to claim 1, wherein at said temperature T 1 Above and said temperature T 2 The sum of the maximum point loads of the pair of support films is greater than the maximum point load of the liquid crystal polymer film at any temperature within the following range.
3. The 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, wherein, at said temperature T 1 Above and said temperature T 2 At least one of the pair of support films has an elongation at break of 200% or more at an arbitrary temperature within the following range.
4. The 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, wherein the 3-layer film for stretching a liquid crystal polymer film is wound around a cylinder having an outer diameter of 84.2mm so that one of the surfaces of the support films is in contact with the cylinder, and is deformed at a winding angle of 90 ° or more, and further, when the other one of the surfaces of the support films is in contact with the cylinder, the 3-layer film for stretching a liquid crystal polymer film is wound around the cylinder, and is deformed at a winding angle of 90 ° or more, no peeling occurs between the liquid crystal polymer film and the support film.
5. The 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, wherein the support film is composed of a crystalline resin.
6. The 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, wherein the support film is composed of aromatic polyether ketone or polyester.
7. The 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, wherein the film thickness of the support film is 5 to 300 μm.
8. A method for producing a 3-layer film for stretching a liquid crystal polymer film, which is the method for producing a 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2, comprising the steps of:
A pair of the support films are laminated on both sides of the liquid crystal polymer film according to a press lamination method or a thermal lamination method.
9. The method for producing a 3-layer film for stretching a liquid crystal polymer film as claimed in claim 8, wherein,
before the step of laminating the liquid crystal polymer film and the support film,
the method comprises the following steps: and carrying out surface treatment on both sides of the liquid crystal polymer film and the surface, which is bonded with the liquid crystal polymer film, of the support film.
10. The method for producing a 3-layer film for stretching a liquid crystal polymer film as claimed in claim 9, wherein,
the surface treatment is any of a plasma treatment, a corona treatment, or a chemical conversion treatment.
11. A method for producing a 3-layer film for stretching a liquid crystal polymer film, which is the method for producing a 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2,
the manufacturing method manufactures the 3-layer film for stretching the liquid crystal polymer film by a melt extrusion method.
12. A method for producing a stretched 3-layer film, comprising the steps of: the 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2 is stretched at least 2.0 to 5.0 times in the TD direction in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
13. The method for producing a stretched 3-layer film according to claim 12, wherein,
after the step of stretching the 3-layer film for stretching a liquid crystal polymer film, the method further comprises the steps of: heat treatment is performed in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
14. A method for producing a stretched liquid crystal polymer film, comprising the steps of: the support film is peeled from the stretched 3-layer film produced by the method for producing a stretched 3-layer film according to claim 12.
15. A method for producing a stretched liquid crystal polymer film, comprising the steps of: a step of peeling the support film from the stretched 3-layer film produced by the method for producing a stretched 3-layer film according to claim 12; and a step of performing heat treatment in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
16. A stretched 3-layer film obtained by stretching the 3-layer film for stretching a liquid crystal polymer film according to claim 1 or 2,
regarding the breaking load measured in 2 directions for the stretched liquid crystal polymer film obtained by peeling the support film, the ratio of the larger breaking load to the smaller breaking load is 6 or less.
17. A stretched liquid-crystalline polymer film produced by the method for producing a stretched liquid-crystalline polymer film according to claim 14,
regarding the breaking load measured in 2 directions for the stretched liquid crystal polymer film, the ratio of the larger breaking load to the smaller breaking load is 6 or less.
18. The stretched liquid crystal polymer film according to claim 17, wherein the melting point of the stretched liquid crystal polymer film is not less than the melting point of the liquid crystal polymer film before stretching.
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