CN101466541A - Laminate, fluid transfer pipe and pipe - Google Patents

Abstract

Disclosed is a multilayer body having excellent visibility and low chemical permeability. Also disclosed are a fluid transport pipe and a tube, each made of such a multilayer body. Specifically disclosed is a multilayer body having a melt-processable fluorine-containing polymer layer (A) and a colored layer (B). This multilayer body is characterized in that the colored layer (B) contains a chlorotrifluoroethylene copolymer and a coloring agent. The chlorotrifluoroethylene copolymer contains at least a chlorotrifluoroethylene unit, a tetrafluoroethylene unit, and a monomer [alpha] unit derived from a monomer [alpha] which is copolymerizable with chlorotrifluoroethylene and tetrafluoroethylene. The chlorotrifluoroethylene unit and the tetrafluoroethylene unit are 90-99.9 mol% in total, and the monomer [alpha] unit is 0.1-10 mol%.

Description

Laminates, fluid transfer tubes and tubes

technical field

The present invention relates to laminates and fluid transfer pipes and tubes using the laminates.

Background technique

Laminates made of fluoropolymers are excellent in chemical resistance, heat resistance, etc., and are used in various manufacturing fields such as semiconductors, liquid crystal panels, pharmaceuticals, and food and beverages.

Among them, in the manufacture of semiconductors and liquid crystal panels, various reagents with strong corrosive effects and liquids with surfactants containing abrasives are used. For the transport of these reagents, it is known to use tubes composed of tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymers [PFA]. This is mainly due to its excellent corrosion resistance and transparency that can observe the transmission status of the fluid.

Several pipes made of PFA are used in a production line, and it is required to be able to easily observe what fluid flows through each pipe (namely, visibility).

In response to such demands, a resin composition in which a mixture of PFA and an inorganic pigment is further mixed with a fluorine-containing organopolysiloxane compound and a molded article thereof are disclosed (for example, see Patent Document 1). However, there is a problem in this molded article that the contained pigment becomes a source of contamination in the production lines of semiconductors and liquid crystal panels.

Then, there is a proposal of a fluid transfer tube having a melt-processable fluoropolymer layer (A) and a colored melt-processable polymer layer (B) in a laminated form (for example, see Patent Document 2). However, there is a demand to further reduce the permeability of the reagent in terms of the permeability of the reagent. Also, in fluid transfer tubing, when the bonding strength of the two layers is low or the two layers are not bonded at all, the reagent permeability may become unsatisfactory.

In addition, a chlorotrifluoroethylene copolymer has been proposed as a fluorine-containing resin having low reagent permeability (for example, see Patent Document 3). Furthermore, there is also a proposal of a fluid transport member composed of a laminate using a chlorotrifluoroethylene copolymer (for example, see Patent Document 4). However, there is no specific description on the coloring of chlorotrifluoroethylene copolymers in any of the above documents.

Patent Document 1: Japanese Patent Laid-Open No. 2000-26688

Patent Document 2: International Publication No. 2005/047747 Pamphlet

Patent Document 3: International Publication No. 2005/100420 Pamphlet

Patent Document 4: International Publication No. 2005/108051 Pamphlet

Contents of the invention

An object of the present invention is to provide a laminate capable of exhibiting excellent visibility and low reagent permeability, and a fluid transport pipe and tube composed of the laminate.

The present invention relates to a laminate comprising a melt-processable fluoropolymer layer (A) and a colored layer (B), wherein the colored layer (B) contains chlorotrifluoroethylene copolymerized and a coloring agent, the above-mentioned chlorotrifluoroethylene copolymer is composed of at least chlorotrifluoroethylene unit, tetrafluoroethylene unit, and monomer [α] derived from monomer [α] that can be copolymerized with chlorotrifluoroethylene and tetrafluoroethylene ] unit as a structural unit, the sum of the above-mentioned chlorotrifluoroethylene unit and the above-mentioned tetrafluoroethylene unit is 90 to 99.9 mol%, and the above-mentioned monomeric [α] unit is 0.1 to 10 mol%.

The present invention relates to a fluid transmission tube, characterized in that it is formed using the above-mentioned laminated body.

The present invention relates to a pipe characterized in that it is formed using the above-mentioned laminated body.

The present invention relates to a semiconductor manufacturing apparatus comprising the above-mentioned fluid transfer pipe or the above-mentioned pipe.

The present invention relates to a reagent supply system for a semiconductor production line, characterized in that it has the above-mentioned fluid transfer tube or the above-mentioned tube.

The present invention will be described in detail below.

The laminate of the present invention has a melt-processable fluoropolymer layer (A) and a colored layer (B).

In this specification, "has a melt-processable fluoropolymer layer (A) and a colored layer (B)" means that the above-mentioned melt-processable fluoropolymer layer (A) and the above-mentioned colored layer (B) can be in contact with each other, However, it is not required that the above-mentioned melt-processable fluoropolymer layer (A) is in constant contact with the above-mentioned colored layer (B). have other layers.

Here, the other layers are not necessarily required to satisfy the performance of the gas barrier layer described later, and can be selected from known materials according to the required performance.

In this specification, the so-called "having a melt-processable fluoropolymer layer (A) and a colored layer (B)" also means that the colored layer (B) covers the entire melt-processable fluoropolymer layer (A) or Set the other layers above.

The above-mentioned colored layer (B) may be a colored layer having all colored parts, or may be a colored layer partially having a colored part and being partially transparent except for the colored part.

In the above laminate, both the melt-processable fluoropolymer layer (A) and the colored layer (B) may be located on the inner layer side.

In the laminate of the present invention, the melt-processable fluoropolymer layer (A) is usually composed of a melt-processable fluoropolymer.

The aforementioned melt-processable fluoropolymer is a polymer having melt-processability in which at least one hydrogen atom bonded to a carbon atom is substituted with a fluorine atom.

Examples of the melt processable fluoropolymer include chlorotrifluoroethylene polymers, vinyl fluoride polymers, and vinylidene fluoride polymers, and tetrafluoroethylene copolymers are more preferred from the viewpoint of corrosion resistance and processability. .

In the present specification, the above-mentioned melt processability refers to a polymer property capable of measuring the melt index at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.

The above-mentioned tetrafluoroethylene copolymer is a copolymer obtained by copolymerizing tetrafluoroethylene [TFE] with a fluoroolefin other than TFE and/or a non-fluorine-containing ethylenic monomer.

In the above-mentioned TFE copolymer, the ratio of the above-mentioned TFE unit to all the monomer units constituting the above-mentioned TFE copolymer is preferably 80 to 99 mol%. If the ratio is less than 80 mol%, the heat resistance may deteriorate, and if it exceeds 99 mol%, the copolymer may become brittle and may cause problems in crack resistance. A more preferable lower limit of this ratio is 85 mol%, and a more preferable lower limit is 90 mol%.

In the present specification, the above-mentioned "all monomer units" means all parts derived from monomers in the molecular structure of the above-mentioned TFE copolymer.

In the present specification, the above-mentioned "TFE unit" refers to a part derived from a TFE monomer in the molecular structure of the above-mentioned TFE copolymer.

Fluoroolefins other than the above-mentioned TFE are not particularly limited, and examples thereof include hexafluoropropylene [HFP], perfluoro(alkyl vinyl ether) [PAVE],

 CF₂＝CFO(CF₂)₂CF＝CF₂

CF ₂ =CFO(CF ₂ ) ₂ CF=CF ₂

Perfluoro ethylenic monomers such as vinylidene fluoride [VdF], trifluoroethylene, fluoroethylene, trifluoropropylene, pentafluoropropylene, tetrafluoropropylene, hexafluoroisobutylene and other hydrogen-containing fluoroethylenic monomers; Chlorine-containing fluoroethylenic monomers such as chlorotrifluoroethylene [CTFE], etc.

From the viewpoint of crack resistance and cost of the obtained resin, perfluoro(propyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(methyl vinyl ether), etc. can be suitably used as the above-mentioned PAVE.

Fluoroolefins other than TFE mentioned above can be used alone or in combination of two or more.

The above-mentioned non-fluorine-containing ethylenic monomers are not particularly limited, and examples thereof include α-olefin monomers having 2 to 10 carbon atoms such as ethylene [Et], propylene, butene, and pentene; methyl vinyl ether , ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, butyl vinyl ether and other alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group, and the like.

The above non-fluorine-containing ethylenic monomers may be used alone or in combination of two or more.

As the above-mentioned tetrafluoroethylene copolymer, TFE is preferable because it can be made into a laminate that is particularly excellent in corrosion resistance and chemical resistance, does not contaminate the internal fluid when used as a fluid transfer tube, and has a high visible light transmittance. /PAVE copolymer [PFA], TFE/HFP copolymer [FEP], Et/TFE copolymer, or TFE/VdF copolymer, more preferably PFA.

When the obtained laminate is used as a fluid transfer tube, and when UV irradiation is performed from the outside of the transfer tube to sterilize fluids such as milk, heat resistance is required, and it is difficult to multiply miscellaneous bacteria. Considering it, it is more preferably PFA.

As the above-mentioned melt-processable fluorine-containing polymer, it is preferable that an unstable terminal does not remain from the viewpoint of chemical resistance. In this specification, the term "unstable terminal" refers to a terminal group that is easily decomposed by heat, such as -COF, -CH ₂ OH, -CONH ₂ , -COOH.

In particular, PFA in which unstable terminals such as -COF, -CH ₂ OH, and -CONH ₂ do not remain is preferable from the viewpoint of chemical resistance. The terminal group of the melt-processable fluoropolymer is preferably -CF ₃ .

The aforementioned melt-processable fluoropolymer may be a product obtained by polymerizing a functional group-containing ethylenic monomer as a comonomer.

In particular, when the above-mentioned melt-processable fluoropolymer is a tetrafluoroethylene [TFE] copolymer, for the purpose of improving the adhesiveness with the colored layer (B) or the gas barrier layer (C) described later, It may be a product obtained by polymerizing an ethylenic monomer containing a functional group as a comonomer.

In this specification, the above-mentioned "ethylenic monomer containing a functional group" refers to a monomer having a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, an alkoxycarbonyl group, and/or an epoxy group as a functional group, and is a monomer having a direct bond An ethylenically unsaturated compound with a fluorine atom on a carbon atom.

As the functional group-containing ethylenic monomer, a vinyl monomer represented by the following general formula (I) is preferable.

CX ¹ ₂ ＝CX ² -Rf ¹ -Y (I)

(In the formula, Y represents a hydroxyl group, a carboxyl group, a carboxyl group forming a salt, an alkoxycarbonyl group or an epoxy group, X ¹ and X ² are the same or different, represent a hydrogen atom or a fluorine atom, Rf ¹ represents that the number of carbon atoms is 1 to 40 fluorine-containing alkylene or a fluorine-containing alkylene group having 1 to 40 carbon atoms having an ether bond.)

As the above-mentioned functional group-containing ethylenic monomer, various compounds represented by the following formulae, etc. are more preferable.

When the functional group-containing ethylenic monomer is used as a comonomer, the ratio of the functional group-containing ethylenic monomer unit to the total monomer units constituting the TFE copolymer is preferably 0.002 to 30 moles. %. If this ratio is less than 0.002 mol%, the copolymerization effect by the said functional group containing ethylenic monomer will fall below the detectable lower limit. A more preferable lower limit of this ratio is 0.01 mol%, and a more preferable lower limit is 0.05 mol%.

In the present specification, the above-mentioned "all monomer units" means all parts derived from monomers in the molecular structure of the above-mentioned TFE copolymer.

In the present specification, the above-mentioned "functional group-containing ethylenic monomer unit" refers to a portion derived from a functional group-containing ethylenic monomer in the molecular structure of the above-mentioned TFE copolymer.

The ratio of the above-mentioned "functional group-containing ethylenic monomer unit" is determined by ¹⁹ F-NMR analysis, infrared spectrophotometry [IR], elemental analysis, and fluorescent X-ray analysis according to the type of functional group-containing ethylenic monomer unit. Combining the values obtained from the analysis.

The above-mentioned melt-processable fluoropolymer layer (A) may contain a colorant as long as it does not dissolve into the reagent used. As a coloring agent in this layer, what is mentioned as a coloring agent contained in the coloring layer (B) mentioned later is mentioned.

The thickness of the above-mentioned melt-processable fluoropolymer layer (A) is not particularly limited, and can be appropriately adjusted to an extent that sufficient visible light transmittance can be exhibited, and is preferably 0.01 to 3.5 mm.

The above colored layer (B) contains a CTFE copolymer and a colorant.

From the aspect of being used in the colored layer (B), the CTFE copolymer in the above-mentioned colored layer (B) is a different concept from the CTFE copolymer in the melt processable fluoropolymer layer (A), but as long as the following The aforementioned requirements regarding the structural unit and its content do not exclude CTFE copolymers having the same composition as the melt-processable fluoropolymer layer (A).

The above-mentioned CTFE copolymer has at least a chlorotrifluoroethylene unit [CTFE unit], a tetrafluoroethylene unit [TFE unit], and a monomer [α] unit derived from a monomer [α] that can be copolymerized with CTFE and TFE as structural units .

In this specification, the above-mentioned "CTFE unit" and _" TFE unit" are the moiety [-CFCl-CF ₂ -] derived from CTFE and the moiety [-CF ₂ -CF 2 -] derived from TFE, respectively, in the molecular structure of the CTFE copolymer. -], the above-mentioned "monomer [α] unit" is a part formed by addition of monomer [α] in the molecular structure of CTFE copolymer.

The above-mentioned monomer [α] is not particularly limited as long as it is a monomer that can be copolymerized with CTFE and TFE, and ethylene [Et], vinylidene fluoride [VdF], perfluoro(alkyl vinyl ether) [ PAVE], a vinyl monomer represented by the following general formula (II), an alkyl perfluorovinyl ether derivative represented by the following general formula (III), and the like.

CX ³ X ⁴ ＝CX ⁵ (CF ₂ ) _n X ⁶ (II)

(In the formula, X ³ , X ⁴ and X ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom, X ⁶ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10.)

CF ₂ =CF-OCH ₂ -Rf ² (III)

(In the formula, Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)

As the above-mentioned monomer [α], unsaturated carboxylic acids copolymerizable with CTFE and TFE described in International Publication No. 2005/100420 pamphlet may also be used.

The aforementioned monomer [α] is preferably at least one selected from the group consisting of Et, VdF, PAVE, and vinyl monomers represented by the aforementioned general formula (II).

The above-mentioned CTFE copolymer is a copolymer obtained by adding TFE as an essential monomer and adding the above-mentioned monomer [α] in a specific ratio described later, so it is a copolymer capable of improving heat resistance, moldability, stress crack resistance, Chemical resistant CTFE copolymer.

The aforementioned CTFE copolymer has not only gas barrier properties and low water vapor permeability, but also low permeability to liquids such as reagents.

In the above-mentioned CTFE copolymer, the above-mentioned monomer [α] unit is 0.1 to 10 mol%, and the total of the CTFE unit and the above-mentioned TFE unit is 90 to 99.9 mol%. When the [α] unit of the above-mentioned monomer is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be poor, and when it exceeds 10 mol%, it has low reagent permeability, heat resistance, and mechanical properties. , productivity, etc. tend to deteriorate.

When the monomer [α] is PAVE, the more preferable lower limit of the monomer [α] unit is 0.5 mol%, the more preferable upper limit is 5 mol%, and the more preferable upper limit is 3 mol%.

The ratio of each monomer unit in the above-mentioned CTFE copolymer is measured by the same method as the ratio of the above-mentioned functional group-containing ethylenic monomer unit.

Examples of CTFE copolymers in the present invention include CTFE/TFE/HFP copolymers, CTFE/TFE/VdF copolymers, CTFE/TFE/PAVE copolymers, CTFE/TFE/HFP/PAVE copolymers, and CTFE/TFE copolymers. /VdF/PAVE copolymer, CTFE/TFE/Et copolymer, CTFE/TFE/Et/PAVE copolymer, etc. Among them, CTFE/TFE/PAVE copolymer is preferred.

The aforementioned CTFE copolymer may be a polymer constituting either a resin or an elastomer, and is preferably a polymer constituting a resin.

As the CTFE copolymer, a copolymer having the physical properties described in International Publication No. 2005/100420 pamphlet is preferable.

In the above-mentioned colored layer (B), it is preferable that the colorant is a colored pigment.

There are no particular limitations on the types of the above-mentioned colored pigments (hereinafter simply referred to as "pigments"). For example, carbon, titanium dioxide, iron oxide red, mica, cobalt oxide, bismuth oxide, antimony white, silicon oxide, etc. can be used alone or in combination. Acid-coated chrome yellow (ケイ acid-coated yellow lead), silicic acid-coated molybdenum orange (ケイ acid-coated モリブデ-トリンジ), silicic acid-coated iron oxide (ケイ acid-coated iron oxide), cadmium red, cadmium orange, cadmium Inorganic pigments such as yellow, ultramarine blue, cobalt, violet, and chromium oxide; organic pigments such as phthalocyanine-based pigments and perylene-based pigments, etc.

As the above-mentioned pigments, it is preferable not to contain cadmium, lead, and cobalt under the background of the EU Directive on Waste Electrical and Electronic Equipment [WEEE], the ban on the use of specific substances [RoHS], etc. PRTR) designation], antimony [PRTR designation], etc., preferably use pigments containing titanium, nickel, niobium, etc. as their substitutes.

The above-mentioned pigment depends on the kind of the pigment used, but from the viewpoint of the visibility of the obtained laminate, it is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the above-mentioned CTFE copolymer.

Regarding the above-mentioned colored layer (B), as the whole colored layer, a colored layer composed of a matrix in which a pigment is uniformly dispersed, a colored layer in which a pigment is uniformly dispersed by performing surface treatment such as etching on the surface layer, etc., as a part Examples of the colored layer include a colored layer in which a pigment is arranged to form a pattern and the other part is transparent; The colored film sheet prepared separately may be a colored layer in which the surface layer is patterned, a colored layer in which a pigment is loaded like printing to form a pattern in the surface layer, etc., may be any of these colored layers, but from the viewpoint of durability, A colored layer composed of a matrix in which a pigment is uniformly dispersed, that is, a colored layer composed of a CTFE copolymer and dispersed with a pigment is preferred.

In this specification, the concept of the above-mentioned "pattern" includes, in addition to the usual patterns such as stripes, blisters, and spirals, numbers such as Arabic numerals and Roman numerals; letters, Chinese characters, hiragana, katakana, and other characters.

In the above-mentioned colored layer (B), in addition to the above-mentioned CTFE copolymer and colorant, resins other than the CTFE copolymer may be contained as needed. The content of resins other than the CTFE copolymer is within a range that does not affect the characteristics of the present invention, and is preferably 10% by mass or less of the total amount of resins in the colored layer (B).

As said resin, TFE/HFP copolymer [FEP] etc. are mentioned, for example.

When mixing the above-mentioned CTFE copolymer and the colorant, any method of wet mixing or dry mixing can be used.

A twin-screw extruder, a Henschel mixer, a tumble mixer, etc. are used for the above-mentioned dry mixing.

In order for the obtained laminate to satisfy the visible light transmittance in the above-mentioned range, the particle diameter of the above-mentioned mixed pigment is preferably 0.1 to 2 μm.

The particle diameter of the pigment after mixing is the average particle diameter measured by the laser light scattering method.

The above-mentioned material for the colored layer (B) can also be prepared by using colored particles as a masterbatch and mixing non-colored particles.

The said colored layer (B) may have a conductive substance as mentioned later.

The thickness of the colored layer (B) is preferably, for example, 0.01 mm to 3.5 mm. When it is less than 0.01 mm, the scratch hardness of the obtained laminate may deteriorate, and when it exceeds 3.5 mm, the visibility of the obtained laminate may deteriorate.

A more preferable upper limit of the above-mentioned thickness is 3 mm, and an even more preferable upper limit is 1.6 mm. When it is within the above-mentioned range, the thickness may be 0.5 mm or more.

In the structure of the laminate of the present invention, when the melt-processable fluoropolymer layer (A) constitutes the innermost layer and the colored layer (B) is arranged on the outer layer side, it is easy to distinguish from other tubes. , can observe the flow condition of the internal fluid, and can also play the effect of not polluting the fluid which will be described later.

The laminate of the present invention may have a gas barrier layer (C) in addition to the melt-processable fluoropolymer layer (A) and the colored layer (B) described above.

In the laminate of the present invention, the pigment does not migrate from the colored layer (B) to the melt-processable fluoropolymer layer (A), but is considered to be a component that permeates out of the melt-processable fluoropolymer layer (A) May cause discoloration of the colored layer (B).

In particular, when the laminate of the present invention is used as a fluid transport tube for transporting gas components, in order to prevent discoloration of the colored layer (B), it is preferable that the melt-processable fluoropolymer layer (A) and the colored layer ( Between B) a gas barrier layer (C) is appropriately provided.

The material of the gas barrier layer (C) is not particularly limited, for example, polyvinyl alcohol and ethylene/vinyl alcohol copolymers are examples of materials excellent in oxygen barrier properties; Materials, such as polychlorotrifluoroethylene [PCTFE], ethylene/chlorotrifluoroethylene copolymer, polyacrylonitrile [PAN]; polyethylene terephthalate [PET], polybutylene terephthalate Alcohol ester [PBT], polyethylene naphthalate [PEN], polybutylene naphthalate [PBN] and other polyesters containing aromatic rings; polyphenylene sulfide [PPS]; polyglycolic acid [PGA ]; polyvinyl chloride [PVC]; polyvinylidene chloride [PVDC]; polyvinyl fluoride [PVF]; The thickness of the barrier layer (C) can also be freely selected according to the composition of the above-mentioned layer (A) and layer (B).

In the laminate of the present invention, the colored layer (B) may be the outermost layer, and a coating layer (D) may be further provided on the colored layer (B).

As the coating layer (D), it is preferred to be a protective layer for protecting the colored layer (B), and in order to have an antistatic effect while having the function of protecting the colored layer (B), or to replace the protective colored layer (B), ) to have an antistatic effect, and the above coating layer (D) may also be a conductive layer.

The material of the coating layer (D) is not particularly limited, and examples thereof include polyurethane resins; polyester resins; aramid resins; polyimide resins; polyamide-imide resins; polyamide-based resins; Resins; polycarbonate resins; acrylic resins; styrene resins; acrylonitrile/butadiene/styrene resins; polyolefin resins such as polyethylene resins, polypropylene resins, and vinyl chloride resins; cellulose resins; Polyvinyl alcohol resins; resins composed of ethylene/vinyl alcohol copolymers, etc. Among them, from the viewpoint of processability and also in order to avoid deterioration of the resin, it is preferable to use a material having a melting point close to that of the fluororesin of the inner layer.

When the above-mentioned coating layer (D) is a conductive layer, the above-mentioned material is usually a material containing a conductive substance, and the above-mentioned conductive substance is not particularly limited, and examples thereof include carbon black, acetylene black, and carbon fiber.

The amount of the conductive substance to be added to the conductive layer is as long as the visible light transmittance of the obtained laminate is 25% or more with respect to the visible light from all peripheral directions, or the outer surface of the obtained laminate is Among them, the area where the visible light transmittance is 25% or more may be in the range of 90% or more of the entire outer surface area.

In the laminate of the present invention, the above-mentioned melt-processable fluoropolymer layer (A) and colored layer (B), and the gas barrier layer (C) and/or coating layer (D) laminated as needed The lamination method is not particularly limited, as long as it is a conventionally known method. For example, when the laminate is a tube, it is conceivable to prepare each layer separately and insert the inner layer inside the outer layer, or to cover the outer layer of the inner layer with a heat-shrinkable tube outer layer; the material of the inner layer In the case of a material whose melting point is higher than that of the outer layer, it is conceivable to use a cross die to melt and coat the outer layer on the inner layer tube like wire overmolding; as the material of the outer layer, use a material that can be dissolved such as PVdF In this case, the method of immersing the inner layer pipe in the paint in which the outer layer material is dissolved, drying it appropriately, and then firing it may be considered. In order to control the cost and maintain a high degree of cleanliness, the simultaneous multi-layer molding method is usually used.

In this specification, the said "outer layer" is used in combination with the term of an inner layer, and it is a layer located outside with respect to an inner layer.

In the laminate of the present invention, an inorganic coating layer may be vapor-deposited on the surface of the melt-processable fluoropolymer layer (A), or a sputtering treatment may be performed on the surface of the above-mentioned melt-processable fluoropolymer layer (A). On the basis of , a coloring layer (B) or a gas barrier layer (C) is provided.

Evaporation and sputtering of the above coatings are less preferred in terms of cleanliness and cost, but in the case of fluid transfer tubes, prevent internal fluid penetration into the melt processable fluoropolymer layer (A ) is sometimes preferred.

In the laminate of the present invention, the above-mentioned colored layer (B) is made of a CTFE copolymer, and after melt molding using a material composed of a CTFE copolymer, or applying a dispersion or a powder coating and firing After the production, even if the shape of the particles made of the melt-processable polymer before firing can be maintained, the shape of the particles of the CTFE copolymer usually disappears, so the adhesiveness is excellent. In addition, especially in the case where the melt-processable fluoropolymer layer (A) is in contact with the above-mentioned colored layer (B), the laminate of the present invention exhibits excellent adhesiveness, and thus can be made to be less prone to delamination. layered body.

Furthermore, in the case where the gas barrier layer (C) is laminated between the colored layer (B) and the melt-processable fluoropolymer layer (A), it is also possible to select a layer that is compatible with the melt-processable fluoropolymer layer (A). The adhesiveness of the material layer (A) and the adhesiveness with the coloring layer (B) are used as the material of the gas barrier layer (C) to form a three-layer tube that is not easy to peel off.

Although the colored layer (B) contains a colorant in addition to the CTFE copolymer, the laminate of the present invention is excellent in visibility and also excellent in reagent permeability.

The 35% hydrochloric acid permeability coefficient of the laminate of the present invention is preferably less than 4.5×10 ^-13 [(g·cm)/(cm ² ·sec)], more preferably less than 1.0×10 ^-13 [(g·cm)/ (cm ² ·sec)], the lower limit of which is not particularly limited, and may be 1.0×10 ^-15 [(g·cm)/(cm ² ·sec)] or more. The lower limit of the transmission coefficient of 35% hydrochloric acid can be set as lower value.

The 35% hydrochloric acid permeability coefficient in this specification is a value measured according to the method described in International Publication No. 2005/100420 pamphlet. method to measure.

[Measuring method of 35% by mass hydrochloric acid permeability coefficient]

The tube to be measured was cut into a length of 30 cm, one end of the tube (1) was sealed with heat, 52 ml of 35% by mass hydrochloric acid was added to the tube (1), and the other end of the tube was also sealed. The tube (1) containing hydrochloric acid was inserted into the glass tube (2), and fixed with a sealing plug (3) made of fluororubber. Then, add 110ml of pure water from the sampling port (4), and place it in a constant temperature bath at 25°C. At this time, the tube between the sealing plugs (3) was in contact with pure water, and the length of the liquid-contacting portion was 18.5 cm. Leave it in this state, sample about 1 ml from the sampling port (4), and use an ion chromatograph (trade name: IC7000-E, manufactured by Yokogawa Electric Co., Ltd.) to measure the chloride ion concentration Y (ppm) contained in the pure water. Quantitatively, calculate with the following formula.

X=(β×film thickness)/cross-sectional area

X: hydrochloric acid permeability coefficient [unit: (g cm)/(cm ² sec)]

β: When α is plotted against T, the slope during which α changes linearly with respect to T (Tβ) (unit: g/sec)

α: Total amount of permeation (unit: g) = Y×W×10 ^-6

W: pure water volume (unit: ml)

T: Elapsed time from the start of penetration to sampling (unit: second)

Film thickness: the thickness of the tube (unit: cm)

Cross-sectional area: In the permeation tester, the area of the part of the tube in contact with pure water (unit: cm ² ).

In the laminate of the present invention, in order to avoid problems such as an increase in the reagent permeability coefficient over time and a decrease in mechanical properties associated with long-term use, the coloring layer (B) and the melt-processable fluorine-containing polymer In the case where the material layers (A) are in contact, the initial bonding strength between the layers is preferably more than 20N/cm, more preferably more than 25N/cm, and the upper limit of the initial bonding strength is not particularly limited, and can be set to 70N /cm.

For the above-mentioned initial adhesive strength, the upper limit temperature (Td) of forming and the melting point (Tm) detected by differential scanning calorimetry [DSC] with a change of less than 5% in the MFR between each layer under the condition of exposure for more than 10 minutes ) has a great relationship, the Td of the resin with the lower melting point in the two layers bonded together must at least exceed the Tm of the resin with the higher melting point. The resin of each layer preferably selects a structural unit according to this characteristic.

For a laminate that is not used after production, the initial adhesive strength can be evaluated in accordance with the adhesive strength measurement described in WO 2005/100420 pamphlet. For example, when the laminate is a tube, it can be evaluated as follows.

(Determination of initial bond strength)

Cut a 1cm-wide sample from the tube, and use a Tensilon universal testing machine to perform a 180°peel test at a speed of 25mm/min, and set the average value of the maximum 5 points in the elongation-tensile strength curve as the initial bond strength.

For the laminate of the present invention, as long as the visible light transmittance is usually 5% or more (preferably 25% or more) with respect to the visible light from all peripheral directions, or the visible light transmittance in the outer surface of the obtained laminate is Usually, the area of the portion of 5% or more (preferably 25% or more) may be in the range of 90% or more of the entire outer surface area.

In the present specification, the visible light transmittance is measured according to the method described in International Publication No. 2005/047747 pamphlet.

The fluid transfer tube of the present invention is formed using the above-mentioned laminate of the present invention.

In this specification, the fluid may be any of gas and liquid, and the liquid may be a volatile liquid or a fluid containing solid particles such as abrasives. The above-mentioned fluid is not particularly limited, and examples thereof include food and drink such as milk, gas, and reagents.

The above-mentioned gas is not particularly limited, and examples thereof include ozone, hydrogen, oxygen, and low-molecular-weight fluorocarbons, which may be gases used in the semiconductor manufacturing field.

The above reagents are not particularly limited, and examples include organic acids such as acetic acid, formic acid, cresol, and phenol; inorganic acids such as hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid; peroxides such as hydrogen peroxide; phosphoric acid-hydrogen peroxide, Sulfuric acid-hydrogen peroxide and other inorganic acids mixed with hydrogen peroxide; alkali solutions such as sodium hydroxide, potassium hydroxide and ammonia water; alcohols such as methanol and ethanol; amines such as ethylenediamine, diethylenetriamine and ethanolamine; amides such as acetamide; esters such as ethyl acetate and butyl acetate; hydrocarbon solvents such as xylene; chlorine solvents such as trichlorethylene; ketones such as acetone; ozone water; ultrapure water; functional water; among these Liquids such as mixtures of two or more types.

The above-mentioned functional water is a liquid obtained by dissolving hydrogen and ammonia in ultrapure water in the field of semiconductor manufacturing.

In the fluid delivery tube of the present invention, it is preferable that the pigment contained in the colored layer (B) is not mixed into the fluid flowing through the fluid delivery tube from the cross section when it is cut for piping construction, repair, and the like.

As a method of preventing the pigment from being mixed into the fluid from the cross-section of the fluid delivery tube, for example, a method including using a joint at the end of the fluid delivery tube with a structure in which the fluid does not directly contact or a method of directly welding the ends of the fluid delivery tube to each other, etc. .

Examples of the "method using a joint having a structure in which fluid does not come into direct contact" include, for example, the method disclosed in JP-A-05-322091.

The fluid delivery tube of the present invention can be used to visually identify the type of fluid flowing in the fluid delivery tube from the outside.

By using the fluid delivery tube of the present invention, the above-mentioned identification of the type of fluid can be performed by recognizing the color or pattern of the fluid delivery tube. For example, in the case of using two or more fluid delivery tubes of the present invention, or in the case of using one or more fluid delivery tubes of the present invention and one or more other tubes for fluid delivery, it is predetermined to have What kind of fluid flows through the fluid transmission tube of the present invention of which color or pattern, so that it can be known which fluid transmission tube by visual inspection outside the above-mentioned fluid transmission tube or other tubes (such as a relatively long distance such as a monitor) What kind of fluid is in circulation.

As long as the above-mentioned other tubes can be visually recognized from the outside as tubes different from the fluid transfer tube of the present invention, the type of fluid in the above-mentioned other tubes can be known by predetermining what kind of fluid flows.

As described above, since the fluid transfer tube of the present invention also has the visibility to see the inside of the tube from the outside, it is possible to know what kind of fluid it is and its type from the appearance characteristics such as the coloring of the fluid itself.

The above-mentioned fluid transmission tube has a high visible light transmittance, and can easily visually recognize the circulation state of the fluid from the outside, thereby significantly improving maintainability.

The fluid transfer tube of the present invention may also be used as an identification fluid transfer tube.

The identification fluid delivery tube is used when visually distinguishing it from other fluid delivery tubes other than the identification fluid delivery tube. For the above-mentioned other fluid delivery tubes, regardless of whether it is a fluid delivery tube that meets the requirements of the above-mentioned fluid delivery tube of the present invention or a fluid delivery tube that does not meet the requirements, as long as the color and/or pattern are consistent with the above-mentioned requirements of the present invention Different identification fluid transfer tubes can be used.

The identification fluid delivery tube may have the same color or pattern as the other fluid delivery tubes as long as it can be distinguished from the other fluid delivery tubes.

The above-mentioned other fluid transfer tubes do not necessarily have to be colored, and may be transfer tubes whose entire outer surface area is transparent.

A pipe using the above-mentioned laminate of the present invention is also one of the present inventions.

The tube of the present invention can adopt the same layer structure and application as the above-mentioned fluid transfer tube, and can be applied to, for example, manufacturing equipment and processing equipment in semiconductor production lines, semiconductor manufacturing workshops, semiconductor substrate manufacturing workshops, semiconductor reagent manufacturing workshops, etc. reagent supply system. The above-mentioned tube can also be suitably used in manufacturing equipment, processing equipment, and the like in a crystallization panel production line.

The semiconductor manufacturing apparatus of the present invention has the above-mentioned fluid transfer pipe or the above-mentioned pipe.

The semiconductor manufacturing device is composed of a manufacturing device for manufacturing semiconductors or semiconductor peripheral parts, and a reagent transfer tube for transferring reagents used in the manufacturing device, and the reagent transfer tube may be the fluid transfer tube or the tube.

The aforementioned semiconductor manufacturing device may be a minimum unit that can be distributed in the market as a manufacturing device, or may be a composite device that combines two or more manufacturing devices of the above-mentioned smallest unit.

When the manufacturing device constituting the reagent supply system for a semiconductor production line of the present invention described later can be divided into several marketing units, the semiconductor manufacturing device may be one of the marketing units.

The aforementioned semiconductor manufacturing apparatus is not particularly limited as long as it uses a reagent, and examples thereof include a coater, a CMP apparatus, and a cleaning apparatus.

A reagent supply system for a semiconductor production line of the present invention includes the above-mentioned fluid transfer tube or the above-mentioned tube.

The above-mentioned reagent supply system for a semiconductor production line can be made into a production line system composed of a manufacturing device for manufacturing semiconductors or semiconductor peripheral parts, and the above-mentioned fluid transfer tube or tube for transferring reagents used in the above-mentioned manufacturing device.

Examples of the above-mentioned reagent supply system for a semiconductor production line include a system including the above-mentioned semiconductor manufacturing apparatus and a reagent supply system composed of reagent tanks, pumps, and the like.

The reagent supply system for a semiconductor production line of the present invention includes a system in which two or more manufacturing devices in a manufacturing process (if necessary, the reagent supply system is further connected) are connected using the above-mentioned fluid transfer tube of the present invention or the tube. .

In addition to the above-mentioned semiconductor manufacturing equipment and reagent supply systems for semiconductor production lines, the fluid transfer tube of the present invention and the tube of the present invention can also be suitably used in applications where it is desired to prevent contamination of fluid circulating inside the tube, such as liquid crystal panel manufacturing systems, Pharmaceutical production line system, food and beverage production line system, etc.

The above-mentioned liquid crystal panel manufacturing device is composed of a manufacturing device for manufacturing a liquid crystal panel and a fluid transfer tube or tube for transferring reagents used in the above-mentioned manufacturing device, and the above-mentioned fluid transfer tube or tube may be the fluid transfer tube or tube of the present invention, respectively. Tubes of the invention.

In the above-mentioned liquid crystal panel manufacturing apparatus, the fluid transfer tube or tube for transferring the reagent may have the same configuration as that of the above-mentioned reagent supply system for a semiconductor production line of the present invention.

The laminate of the present invention can exhibit visibility and is excellent in reagent permeability, and the fluid transmission tube and the tube composed of the laminate can easily distinguish a specific fluid transmission tube from other fluid transmission tubes by visual inspection. The pipes are distinguished from each other, and the flow status of the internal fluid can be identified from a certain distance away, without polluting the internal fluid. The fluid transfer tube of the present invention can be suitably used in various manufacturing fields such as semiconductors, liquid crystal panels, pharmaceuticals, and food and beverages.

Description of drawings

FIG. 1 is a diagram showing a method for measuring the transmission coefficient of 35% by mass hydrochloric acid.

Symbol Description

1. tube

2. Glass tube

3. Gasket

4. Sampling port

Detailed ways

The following examples are given to specifically illustrate the present invention, but the present invention is not limited by these examples.

Unless otherwise specified, the amounts of the compositions in Examples and Comparative Examples are based on mass.

In addition, the ratio of monomer units, reagent permeability test, adhesive strength and reagent permeability (35% by mass hydrochloric acid permeability coefficient) were measured in accordance with Example 1 of International Publication No. 2005/100420 pamphlet. The same method as described above is carried out, and the visible light transmittance and liquid level confirmation test (visibility) are measured according to the same method as Example 1 of the International Publication No. 2005/047747 pamphlet, and the coloring and hue are carried out using a color computer (trade name: SM-7, manufactured by SUGA TEST INSTRUMENTS), when the rate of change in numerical value thereof was less than 1.0%, it was considered that there was no change in color tone.

Example 1

(1) Production of mixed particles for coloring layer (B)

Chlorotrifluoroethylene [CTFE] copolymer particles (CTFE:TFE:PPVE=34.5:64:1.5 (mol %)) and PFA colored particles ( Product name: NEOFLON PFA AP-210RD, manufactured by Daikin Industries, Ltd.) mixed (mixing ratio: PFA color particles: CTFE copolymer particles = 1:49).

The obtained mixed pellets were melted and kneaded at 330° C. for 10 minutes, and then molded at 350° C. at a pressure of 5 MPa using a heating molding machine with a hot plate capable of temperature adjustment with an accuracy of ±1° C. Molded sheet with a thickness of 0.2mm.

A reagent permeability test was carried out on the obtained molded sheet. As a result, the 35% by mass hydrochloric acid permeability coefficient was 0.27×10 ^-13 [(g·cm)/ (cm ² ·sec)].

(2) Production of double-layer pipe

Tetrafluoroethylene [TFE]/perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] pellets (trade name: NEOFLON PFA AP231-SH, manufactured by Daikin Industries, Ltd.) were used as the melt-processable fluoropolymer In layer (A), the melt-processable fluoropolymer layer (A) is used as an inner layer, and the colored layer (B) composed of the mixed particles obtained in Example 1 (1) of the present application is used as an outer layer, in addition, A double-layered tube with an outer diameter of 19.1 mm and an inner diameter of 15.9 mm (thickness of the outer layer of 0.2 mm and thickness of the inner layer of 1.4 mm) was fabricated according to Example 1 [Manufacture of Laminated Tube A] of International Publication No. 2005/100420 pamphlet.

The obtained double-layer tube showed sufficient colorability, the accuracy rate in the visibility evaluation was 100%, the visible light transmittance was 25% or more, the bonding strength of the tube was 24 N/cm, and the transmission coefficient of 35% by mass hydrochloric acid It is 0.93×10 ^-13 [(g·cm)/(cm ² ·sec)].

Example 2

Mix 2 mass parts titanium dioxide, aluminum, cobalt series pigment (average particle diameter 0.3 μ m) in 98 mass parts CTFE copolymers described in embodiment 1 (1) of the present application, and then the mixture obtained is mixed (diluted) in 50 times In the CTFE copolymer described in the above-mentioned embodiment 1 (1) of quality. The pigment-dispersed CTFE copolymer particles thus obtained were used as the colored layer for the outer layer. Except for this, a double-layer tube was produced in the same manner as in the above-mentioned Example 1, and evaluated. Visibility and visible light transmittance are the same as in Example 1. The adhesive strength was 29 N/cm, and the transmission coefficient of 35% by mass hydrochloric acid was 0.90×10 ^-13 [(g·cm)/(cm ² ·sec)].

Example 3

FEP colored particles (trade name: NP-20GN, manufactured by Daikin Industries) and the CTFE copolymer particles recorded in the embodiment of the application 1 (1) are mixed (mixing ratio is FEP colored particles: CTFE copolymer particles=1:49 ), except that the obtained composition was used as a colored layer for the outer layer, a double-layered tube was produced in the same manner as in Example 1 of the present application, and evaluated. Visibility and visible light transmittance are the same as in Example 1 above. The adhesive strength was 27 N/cm, and the transmission coefficient of 35% by mass hydrochloric acid was 0.92×10 ^-13 [(g·cm)/(cm ² ·sec)].

Example 4

The colored layer (B) made of the mixed particles obtained in Example 1 (1) of the present application is used as an inner layer, and the layer composed of PFA particles described in Example 1 (2) of the present application is used as an outer layer. In addition, the The same evaluation as Example 1 of the present application.

The obtained double-layer pipe showed sufficient colorability, the accuracy rate in the visibility evaluation was 100%, the visible light transmittance was 25% or more, the adhesive strength was 26N/cm, and the transmission coefficient of 35% by mass hydrochloric acid was 0.81 ×10 ^-13 [(g·cm)/(cm ² ·sec)].

Example 5

As the outermost layer, a layer made of polychlorotrifluoroethylene (trade name: NEOFLON PCTFE M-300PL, manufactured by Daikin Industries, Ltd.) with a thickness of 0.15 mm is provided outside the colored layer (B). In Example 1 of the application, a melt-processable fluoropolymer layer (A) and a colored layer (B) were provided in the same manner to produce a three-layer pipe. Visibility and visible light transmittance are the same as in Example 1 above. The bonding strength between the innermost layer (A) and the colored layer (B) was 25 N/cm. The bonding strength between the colored layer (B) and the outermost polychlorotrifluoroethylene layer was 21 N/cm. The permeability coefficient of 35% by mass hydrochloric acid is 0.43×10 ^-13 [(g·cm)/(cm ² ·sec)].

Comparative example 1

Extrusion molding is carried out so that the layer made of the CTFE copolymer particles made by the same method as the embodiment of the application 1 (1) is the outer layer, and the layer formed of the PFA particles described in the embodiment 1 of the application is the inner layer. layer, except that, a double-layer tube was produced by the same method as in Example 1 of the present application, and evaluated.

^[ (g·cm)/(cm ² ·sec)].

Comparative example 2

Use the pigment dispersion CTFE copolymer particle that mixes 35 mass parts iron oxide red pigments (average particle diameter 0.17 μm) in 100 mass parts of the CTFE copolymer of the application embodiment 1 as the raw material of the colored layer, and make the outer diameter The double-layer tube was produced under the same conditions as in Example 1 of the present application except that the inner diameter was 25 mm, the inner diameter was 20 mm, the outer layer thickness was 1.0 mm, and the inner layer thickness was 1.2 mm.

In the obtained double-layer tube, the visible light transmittance was less than 5% relative to the visible light from all peripheral directions, and the accuracy of visibility was 32%.

Comparative example 3

The layer made of the PFA particles described in the embodiment of the application 1 (2) is used as an inner layer, and the PFA particles (trade name: NEOFLON PFA AP231-SH, manufactured by Daikin Industry Co., Ltd.) and PFA colored particles (trade name: NEOFLON PFA AP-210RD, manufactured by Daikin Industry Co., Ltd.), the mixture (mixing ratio is PFA color particles: PFA particles=1:49) constitutes the layer as the outer layer, except that it is made in the same manner as Example 1 of the present application Double pipe. The obtained double-layer tube showed sufficient colorability, and the permeability coefficient of 35% by mass hydrochloric acid was 6.13×10 ^-13 [(g·cm)/(cm ² ·sec)].

As described above, the double-layered pipes of Examples 1 to 5 provided with the colored layer having the CTFE copolymer and the pigment exhibited the same effect as the double-layered pipe of Comparative Example 1 provided with the layer using the CTFE copolymer alone (no colorant). Equally good low permeability of reagents, adhesiveness, interlayer adhesion and visibility, and the identification of contents by coloring. In addition, compared with the double-layer tube of Comparative Example 3 in which PFA particles were used instead of the CTFE copolymer in the colored layer, it had significantly excellent low permeability of reagents.

In addition, it can be seen that the tubes of the respective examples have more appropriate thickness and transmitted light intensity than those of Comparative Example 2, and thus can obtain good visibility.

Industrial Applicability

The laminate of the present invention can exhibit good reagent low permeability, adhesiveness, and visibility, and thus can be suitably used as fluid transfer tubes, tubes, especially fluid transfer tubes in reagent supply systems for semiconductor production lines . The fluid transfer tube of the present invention can be suitably used in various manufacturing fields such as semiconductors, liquid crystal panels, pharmaceuticals, and food and beverages.

Claims (13)

1. A laminate comprising a melt-processable fluoropolymer layer (A) and a colored layer (B), wherein the laminate is characterized in that The colored layer (B) contains a chlorotrifluoroethylene copolymer and a coloring agent, The chlorotrifluoroethylene copolymer has at least a chlorotrifluoroethylene unit, a tetrafluoroethylene unit, and a monomer [α] unit derived from a monomer [α] that can be copolymerized with chlorotrifluoroethylene and tetrafluoroethylene as a structure unit, The total of the chlorotrifluoroethylene unit and the tetrafluoroethylene unit is 90 to 99.9 mol%, and the monomer [α] unit is 0.1 to 10 mol%. 2. The laminated body as claimed in claim 1, wherein the 35% hydrochloric acid transmission coefficient of the laminated body is less than 4.5×10 ^-13 [(g·cm)/(cm ² ·sec)], visible light transmits The rate is more than 5%. 3. The laminate according to claim 1 or 2, wherein the 35% hydrochloric acid permeability coefficient of the laminate is less than 1.0×10 ^-13 [(g·cm)/(cm ² ·sec)]. 4. The laminate according to claim 1, 2 or 3, wherein the initial bonding strength between the colored layer (B) and the melt-processable fluoropolymer layer (A) is 20 N/cm or more. 5. The laminate according to claim 1, 2, 3 or 4, wherein the initial bonding strength between the colored layer (B) and the melt-processable fluoropolymer layer (A) is 25 N/cm or more. 6. The laminate according to claim 1, 2, 3, 4 or 5, wherein the colored layer (B) has a thickness of 0.01 to 3.5 mm. 7. The laminate according to claim 1, 2, 3, 4, 5 or 6, wherein the melt-processable fluoropolymer layer (A) is the inner layer, and the colored layer (B) is the melt-processable The outer layer of the permanent fluoropolymer layer (A). 8. The laminate according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the melt-processable fluoropolymer layer (A) is composed of a tetrafluoroethylene copolymer. 9. The laminate according to claim 8, wherein the tetrafluoroethylene copolymer is a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer. 10. A fluid transfer tube, characterized in that it is formed using the laminate as claimed in claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. 11. A pipe characterized in that it is formed by using the laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. 12. A semiconductor manufacturing apparatus comprising the fluid transfer tube according to claim 10 or the tube according to claim 11. 13. A reagent supply system for a semiconductor production line, characterized by comprising the fluid transfer tube according to claim 10 or the tube according to claim 11.

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