JP4945896B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to a composition for forming a non-curable coating film on a fluororesin substrate.

  For example, a fluororesin film has excellent weather resistance, heat resistance, chemical resistance, electrical properties, and mechanical properties, and its transparency and mechanical strength are maintained for a long time. There is an increasing demand for transparent films to be constructed. In recent years, it has also been used as a structural member having a daylighting function for a tent film of an exhibition hall or an arena ceiling.

  In particular, when used for structural members that have daylighting functions, it not only has good weather resistance, which is unlikely to deteriorate in performance even when exposed to the outdoors, but also for improved design as a structure or comfort in the interior space. In addition, it is required that the film itself can be colored and that the lighting rate can be controlled.

Generally, fluororesin film is a material that is difficult to print on the film surface. However, Patent Documents 1 and 2 below propose a method that allows printing using an ink having a pigment or dye on the fluororesin film. Has been.
The following Patent Document 1 describes a method of forming a printing layer (coating film) using a fluorine resin type ink having good weather resistance so as not to impair the original weather resistance of the fluorine-containing resin film. Moreover, it describes that the adhesiveness of a printing layer and a fluororesin film can be improved by carrying out the surface activation process of the to-be-printed surface by corona discharge treatment etc. prior to printing.
In the experimental example of Patent Document 1, ink 1 containing a fluorinated copolymer is used. This fluorinated copolymer has an intrinsic viscosity of 0.4 dL / g. Is estimated to exceed 100,000.

Patent Document 2 listed below describes a method of providing a layer (cured coating film) made of a cured product of a curable fluororesin on a layer made of a fluorine-containing resin.
Japanese Patent Laid-Open No. 3-142237 JP-A-8-11268

As described in Patent Documents 1 and 2, if a method of providing a coating film on a fluorine-containing resin film is used, it is possible to easily control the daylighting rate and to give a design.
However, in recent years, the use of the fluorine-containing resin film has further expanded, and a technique capable of achieving higher adhesion of the coating film, higher weather resistance, and higher moisture resistance is demanded.

  The present invention has been made in view of the above circumstances, and provides a composition capable of forming a coating film excellent in adhesion, weather resistance, and moisture resistance on a fluororesin substrate, and a laminate using the composition. .

In order to solve the above-mentioned problem, the method for producing a laminate of the present invention comprises applying the following non-curable coating film-forming composition to a part or all of the fluororesin substrate, 60 to 150 ° C, The coating film is formed by drying under conditions of 2 to 20 seconds.
Non-curable coating film-forming composition: comprising a fluorine-containing copolymer and a solvent, wherein the fluorine-containing copolymer has a mass average molecular weight (Mw) of 30,000 to 60,000, and the fluorine-containing copolymer polymers one mole per hydroxyl group, a carboxyl group, is less than an amide group and the first average number of moles of total functional groups contained in the functional groups is 33 or more 54 consisting of a glycidyl group, the average moles of said total The ratio of the average number of moles of hydroxyl groups per mole of the fluorinated copolymer to the number is 80% or more.

The non-curable coating film-forming composition preferably contains a coloring component .

It is preferable that the surface of the fluororesin substrate on which the coating film is formed is surface-treated before forming the coating film.

According to the composition for forming a non-curable coating film of the present invention, a coating film excellent in adhesion, weather resistance, and moisture resistance can be formed on a fluororesin substrate.
According to the present invention, a laminate in which a coating film excellent in adhesion, weather resistance, and moisture resistance is provided on a fluororesin substrate is obtained.

<Fluorine-containing copolymer>
The monomer that is a polymerization unit of the fluorinated copolymer in the present invention is a fluorinated monomer having an ethylenically unsaturated group, and examples thereof include tetrafluoroethylene, hexafluoropropylene, perfluorobutene-1, and perfluorohexene-1. , Perfluorononene-1, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, and the like; perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (heptyl) Perfluoro (alkyl vinyl ether) s such as vinyl ether); (perfluoroalkyl) ethylenes such as (perfluoromethyl) ethylene and (perfluorobutyl) ethylene. Various monomers can be used for the vinyl ether component. These fluorine-containing monomers may be used alone or in combination of two or more. The fluorine-containing monomer is preferably a fluoroolefin having 2 to 3 carbon atoms, particularly fluoroethylenes such as tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride.

The fluorine-containing copolymer preferably has a polymer unit based on a polymerizable monomer other than the fluorine-containing monomer. As the polymerizable monomer, a polymerizable monomer in which a hydrogen atom bonded to a carbon atom forming an ethylenically unsaturated group is not substituted with a fluorine atom is preferable. Examples of the polymerizable monomer include vinyl ethers. Especially, the compound which has a C1-C15 linear, branched or alicyclic alkyl group is preferable. These polymerizable monomers may be used alone or in combination of two or more. Specific examples of the polymerizable monomer include the following compounds.
Examples thereof include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, and (perfluoroalkyl) vinyl ether.

  The fluorine-containing copolymer is preferably a copolymer containing 30 to 70 mol% of a polymer unit derived from the fluorine-containing monomer. In particular, it is preferable that the polymer units derived from the fluorine-containing monomer have a ratio of 40 to 60 mol%. When the copolymerization ratio of the fluorine-containing monomer is within the above range, the weather resistance of the coating film is improved.

The fluorine-containing copolymer needs to have a functional group included in the first functional group consisting of a hydroxyl group, a carboxy group, an amide group, and a glycidyl group.
The average number of moles of the total functional groups contained in the first functional group per mole of the fluorinated copolymer is in the range of 33 or more and less than 54. A more preferable range is 34 or more and less than 51.
By setting it above the lower limit of the above range, the adhesion between the coating film and the fluororesin substrate is improved. In particular, when the fluororesin substrate is subjected to the surface treatment described below, a good adhesion improving effect can be obtained. When the average number of moles of the total functional groups contained in the first functional group is less than the upper limit of the above range, the adhesiveness of the coating film is low, it is difficult to adsorb dust in the atmosphere, and the surface of the coating film Is hard to get dirty.

The ratio of the average number of moles of hydroxyl groups per mole of the fluorinated copolymer to the total average number of moles of functional groups contained in the first functional group per mole of the fluorinated copolymer is 80%. Preferably, it is 90% or more, and may be 100%.
By setting the ratio of the average number of moles of the hydroxyl group within the above range, the adhesiveness is excellent when the fluororesin substrate is subjected to a surface treatment described later.

When the fluorine-containing copolymer is produced, a copolymer having a functional group-containing polymer unit is obtained by using a polymerizable monomer containing a functional group.
Specific examples of the polymerizable monomer having a functional group include the following compounds.
Examples of the hydroxyl-containing polymerizable monomer include allyl alcohol; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether; 2-hydroxyethyl allyl ether, 3 -Hydroxyalkyl allyl ethers such as hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 4-hydroxycyclohexyl allyl ether; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; vinyl hydroxyacetate, hydroxy Vinyl isobutyrate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, hydroxycyclohexane Esters of hydroxyalkyl carboxylic acids such as vinyl silcarboxylate and vinyl alcohol; hydroxyalkyl allyl esters such as hydroxyethyl allyl ester, hydroxypropyl allyl ester, hydroxybutyl allyl ester, hydroxyisobutyl allyl ester, hydroxycyclohexyl allyl ester, etc. Can be mentioned.

Examples of the carboxy group-containing polymerizable monomer include (meth) acrylic acid and carboxyalkyl allyl ester.
Examples of the amide group-containing polymerizable monomer include (meth) acrylamide, N-methyl (meth) acrylamide and the like.
Examples of the glycidyl group-containing polymerizable monomer include glycidyl allyl ether and glycidyl (meth) acrylate.

  A polymer unit having a functional group can be converted into a polymer unit having another functional group by reacting with a specific compound. For example, a hydroxyl group-containing polymer unit can be converted to a carboxyl group-containing polymer unit by reacting with a divalent carboxylic acid anhydride such as succinic anhydride.

The fluorine-containing copolymer has a mass average molecular weight (M _w ) of 30,000 to 60,000. 35000 or more and 55000 or less are more preferable, and 40000 or more and 50000 or less are more preferable.
When the mass average molecular weight is not less than the lower limit of the above range, the coating film hardly breaks down.
When the mass average molecular weight is not more than the upper limit of the above range, the heat fluidity is improved, and the wettability at the interface, which is important in improving the adhesion of the coating film, can be secured. Thereby, adhesiveness improves effectively.

The number average molecular weight (M _n ) of the fluorine-containing copolymer is not particularly limited, but is preferably 10,000 or more and less than 35,000 from the viewpoint of good adhesion between the substrate and the coating film and suppression of cohesive failure of the coating film. . 12000 or more and 33000 or less are more preferable, and 12000 or more and 30000 or less are the most preferable.

In the present invention, as a resin component of the composition for forming a non-curable coating film, a resin other than the fluorine-containing copolymer, such as a polyester resin, an acrylic resin, an epoxy resin, etc., as long as the effects of the present invention are not impaired. May be used in combination.
The proportion of the fluorine-containing copolymer in the resin component of the composition for forming a non-curable coating film is preferably 75% by mass or more, and may be 100% by mass.

<Solvent>
The composition for forming a non-curable coating film of the present invention can be prepared by dissolving the fluorine-containing copolymer in a solvent.
Solvents include aromatic hydrocarbons such as xylene and toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone and methyl ethyl ketone, saturated hydrocarbons such as n-hexane and ligroin, HCFC-225 (manufactured by Asahi Glass Co., Ltd., HCFC (hydrochlorofluorocarbon) such as trade name: AK-225). The solvent may be used alone or in combination of two or more.
The solid content concentration of the composition for forming a non-curable coating film of the present invention is not particularly limited, and is preferably about 20 to 70% by mass, depending on the film thickness of the coating film to be obtained, and is preferably 30 to 60% by mass. The degree is more preferred.

<Other ingredients>
A coloring component can be contained in the composition for forming a non-curable coating film. For example, pigments usually used in gravure inks can be blended. Suitable pigments include colored pigments such as organic pigments and inorganic pigments, and bright pigments such as aluminum paste, mica and pearl.
The organic pigment and the inorganic pigment may be of a type coated with a surfactant such as silicon oil or stearic acid in order to improve compatibility with the fluorine-containing copolymer.
In the case of an aluminum paste, in order to improve resistance to water, acid, and alkali, it is preferable to use a type in which an acrylic resin having a high crosslinking density is coated on the surface or a type in which silica is coated on the surface. .
In addition, the pearl pigment coated with titanium oxide on the outermost layer preferably has an inorganic coating layer made of zirconia, alumina, and silica outside the titanium oxide coating layer in order to suppress photoactivity with respect to the fluorine-containing copolymer. Used for.
The amount of the pigment added is preferably 5 to 150 parts by mass and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the fluorine-containing copolymer.

In the composition for forming a non-curable coating film, other components conventionally used for ink can be used as appropriate. For example, other additives usually used in gravure inks can be blended. Specific examples include antioxidants, sagging inhibitors, ultraviolet absorbers, light stabilizers, surface conditioners, slip agents, catalysts, and the like.
The compounding quantity of another additive is suitably selected from the range of 0.01-40 mass parts with respect to 100 mass parts of a fluorine-containing copolymer.

<Substrate>
The substrate in the present invention is made of a fluorine-containing resin having a fluorine content of 45% by mass or more. By setting the fluorine content to 45% by mass or more, good stain resistance, chemical resistance, non-adhesiveness, and weather resistance can be obtained. In particular, sufficient non-adhesiveness and stain resistance can be obtained. The fluorine content is preferably 50% by mass or more, and particularly preferably 55% by mass or more. The substrate is preferably light transmissive and more preferably transparent.
Fluorine-containing resins include ethylene / tetrafluoroethylene copolymer (hereinafter referred to as ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter referred to as FEP), or tetrafluoroethylene / perfluoro (alkyl vinyl ether). A copolymer is preferred. ETFE is particularly preferable.

Examples of the ETFE include ETFE having a molar ratio of tetrafluoroethylene polymerized units / ethylene polymerized units of 30/70 to 70/30, preferably 40/60 to 60/40. As ETFE, in addition to the above two components, one or two or more additional components such as fluorine-containing olefins and / or hydrocarbon olefins may be copolymerized.
Examples of the additional component include α-olefins such as propylene and 1-butene, hexafluoropropylene, vinylidene fluoride, fluorine-containing olefins such as (perfluorobutyl) ethylene and trifluorochloroethylene, and perfluoro (alkyl vinyl ether). And fluorine-containing vinyl ethers, fluorine-containing acrylates, and the like.
As the perfluoro (alkyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (methyl vinyl ether), and perfluoro (propyl vinyl ether) are preferable.
When the additional component is copolymerized, it is preferably copolymerized at 50 mol% or less in ETFE within a range where the fluorine content does not become less than 45% by mass. In some cases, the ETFE may be modified by copolymerizing additional components in a small amount of 10 mol% or less.
In particular, ETFE copolymerized with 0.1 to 2 mol% of (perfluorobutyl) ethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether) as the third component or the fourth component has long-term transparency and mechanical properties. Can maintain strength. Furthermore, the film which shape | molded this ETFE to the thickness of about 100 micrometers-300 micrometers is suitable as a film for structural members.

The molecular weight of ETFE is not particularly limited, but is preferably about 10 to 300 mm ³ / sec as a volume flow rate serving as a guide. The capacity flow rate was measured by using a Koka flow tester at a temperature of 300 ° C., a load of 30 kg / cm ² , and flowing out from a nozzle having a diameter of 1 mm and a length of 2 mm, and the capacity of ETFE flowing out per unit time (seconds) ( mm ³ ).

Examples of the FEP include FEP having a tetrafluoroethylene polymer unit / hexafluoropropylene polymer unit molar ratio of 70/30 to 99/1, preferably 80/20 to 95/5. As FEP, in addition to the above two components, one or two or more additional components such as fluorine-containing olefins and / or hydrocarbon olefins may be copolymerized. As this additional component, α-olefins such as propylene and 1-butene, fluorine-containing olefins such as vinyl fluoride, vinylidene fluoride, (perfluorobutyl) ethylene and trifluorochloroethylene, and perfluoro (alkyl vinyl ether) Fluorine-containing vinyl ethers such as
As the perfluoro (alkyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (methyl vinyl ether), and perfluoro (propyl vinyl ether) are preferable.
When these additional components are copolymerized, the FEP may be modified to a degree that is preferably 10 mol% or less.

The molecular weight of FEP is not particularly limited, but a volume flow rate of approximately 0.5 to 300 mm ³ / second is suitable as a guideline. The volume flow rate was measured by using a Koka flow tester at a temperature of 380 ° C., a load of 7 kg / cm ² , flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm, and the volume of FEP flowing out per unit time (seconds) ( mm ³ ).

The alkyl group in the tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer preferably has 1 to 3 carbon atoms. In particular, a tetrafluoroethylene / perfluoro (propyl vinyl ether) copolymer (hereinafter referred to as PFA) is preferable.
Examples of PFA include PFA having a molar ratio of tetrafluoroethylene polymerized units / perfluoro (alkyl vinyl ether) polymerized units of 80/20 to 99.5 / 0.5, preferably 90/10 to 99/1. Examples of perfluoro (alkyl vinyl ether) include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), and perfluoro (n-heptyl vinyl ether). In view of copolymer physical properties, perfluoro (propyl vinyl ether) is preferred. As PFA, in addition to the above two components, one or two or more small amounts of additional components such as fluorine-containing olefins and / or hydrocarbon olefins may be copolymerized. Examples of the additional component include α-olefins such as propylene and 1-butene, and fluorine-containing olefins such as vinyl fluoride, vinylidene fluoride, (perfluorobutyl) ethylene, trifluorochloroethylene, and hexafluoropropylene. It is done.
When these additional components are copolymerized, it is sufficient to modify PFA, and it is preferable to copolymerize at 10 mol% or less.

The molecular weight of PFA is not particularly limited, but a volume flow rate of about 0.5 to 300 mm ³ / second is suitable as a guideline. The capacity flow rate was measured by using a Koka flow tester at a temperature of 380 ° C., a load of 7 kg / cm ² , flowing out of a nozzle having a diameter of 2 mm and a length of 8 mm, and the capacity of PFA flowing out per unit time (seconds) ( mm ³ ).

  The fluorine-containing resin of the substrate is not particularly limited as long as the fluorine content is 45% by mass or more, and various fluorine-containing resins can be used in addition to the above ETFE, FEP, and PFA. For example, as a highly transparent fluorine-containing resin, a polymer having a fluorine-containing aliphatic ring structure can be mentioned. Examples of the polymer include those obtained by polymerizing monomers having a fluorine-containing ring structure, or those obtained by cyclopolymerizing a fluorine-containing monomer having at least two polymerizable double bonds. And polymers having a group ring structure.

The polymer having a fluorinated aliphatic ring structure in the main chain is obtained by homopolymerizing a monomer having a fluorinated ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole) or the like. It can be obtained by copolymerizing a monomer having a fluorine ring structure and a radical polymerizable monomer such as tetrafluoroethylene (see Japanese Patent Publication No. 63-18964).
The polymer having a fluorinated aliphatic ring structure in the main chain cyclizes a fluorinated monomer having at least two polymerizable double bonds such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether). It can be obtained by polymerization or by copolymerizing this fluorine-containing monomer and a radical polymerizable monomer such as tetrafluoroethylene (see JP-A-63-238111, JP-A-63-238115, etc.).
Furthermore, a polymer having a fluorine-containing aliphatic ring structure in the main chain can also be obtained by copolymerizing a monomer having a fluorine-containing ring structure and a fluorine-containing monomer having at least two polymerizable double bonds. A polymer having a fluorine-containing aliphatic ring structure in the main chain preferably has a ring structure content of 20% by mass or more from the viewpoints of transparency, mechanical properties, and the like.

The thickness of the substrate is not particularly limited, but is preferably 5 to 500 μm in order to obtain high transparency, and is preferably 10 to 200 μm in view of mechanical properties, cost, and the like.
Further, when the substrate is used by being laminated on another substrate, the thickness of the substrate can be further reduced.

<Surface treatment>
In order to obtain good adhesion between the substrate and the coating film, the surface of the substrate on which the coating film is formed is preferably surface-treated before the coating film is formed.
As the surface treatment method, a known method usually used for improving the adhesiveness of the fluorine-containing resin can be appropriately employed. For example, corona discharge treatment, metal sodium treatment, mechanical surface roughening treatment, excimer laser treatment, etc. can be used. In particular, corona discharge treatment is preferable.
In general, in order to obtain good adhesion between the substrate and the coating film, the surface treatment is preferably performed so that the surface tension of the substrate is 0.035 N / m or more, and more preferably 0.04 N / m or more.
By performing the above surface treatment, oxygen functional groups and / or nitrogen functional groups are introduced into the surface of the substrate, and are present in the functional groups on the substrate side and in the fluorine-containing copolymer of the composition for forming a non-curable coating film. It is considered that the adhesion between the substrate and the coating film is improved by forming a chemical bond with a functional group such as a hydroxyl group.

In the corona discharge treatment, it is advantageous in terms of the production process to arrange the corona discharge treatment machine on the production line for producing the fluorine-containing resin substrate and sequentially perform the treatment. The treatment conditions are selected depending on the type of fluororesin substrate to be treated and the desired degree of treatment. Although not particularly limited, it is preferable to perform the treatment at about 0.5 to 100 m ² / min with an intensity of about 0.1 to 10 kW.

<Laminated body>
The laminate of the present invention is obtained by applying the non-curable coating film-forming composition on a fluororesin substrate and drying it to form a coating film.
The coating method can be performed by a common coating method such as gravure printing.
After application, the solvent is volatilized and the film is preferably dried at 60 ° C. to 150 ° C. for 2 seconds to 20 seconds in order to improve the adhesion between the coating film and the substrate.
The coating film may be formed on the entire surface of the substrate or may be formed so as to cover a part of the surface of the substrate.
Moreover, you may provide on one surface of a base | substrate and you may provide a coating film on both front and back surfaces of a base | substrate. Preferably, it is on one side.
The coating film in the present invention is non-curable. The non-curable coating film refers to a coating film in a state where the resin component is not crosslinked. Therefore, the non-curable coating film can be dissolved by contacting the solvent.

According to the present invention, it is possible to obtain a laminate having excellent weather resistance and moisture resistance, which has excellent adhesion between the substrate and the coating film and does not deteriorate in performance even after long-term outdoor exposure.
Moreover, since the coating film provided on the substrate is non-curable, it has excellent followability to deformation of the substrate. Therefore, even if the substrate is repeatedly deformed by wind or a pressure change inside the structure, the coating film is difficult to peel off. On the other hand, a film made of a cured product of a conventional curable fluororesin is difficult to follow the deformation of the substrate due to the shrinkage stress, and interface peeling is likely to occur depending on the application.
Although the use of the laminated body of this invention is not specifically limited, It is suitable for the use especially used outdoors. Specific examples include a tent film in an exhibition hall, a structural member having a daylighting function for an arena ceiling, and agricultural materials.
In addition, the degree of freedom in designing the shape and size of the coating film is high. Therefore, if the substrate is made of a transparent material and the coating film is made of a light-shielding material, the lighting rate can be freely controlled by the shape and size of the coating film.

In order to explain the present invention in more detail, the following examples are given.
(Fluorine-containing copolymer synthesis example 1)
In a pressure resistant reactor with a stainless steel stirrer with an internal volume of 2500 mL, 620 g of xylene, 330 g of ethyl vinyl ether (EVE), 133 g of 4-hydroxybutyl vinyl ether (HBVE), 10 g of potassium carbonate as a buffer, and perbutyl parr as a polymerization initiator 3.5 g of pivalate (PBPV) was charged, and dissolved oxygen in the liquid was removed by solidification and degassing with liquid nitrogen.
Next, 690 g of chlorotrifluoroethylene (CTFE) was introduced, the temperature was gradually raised, and the reaction was continued while maintaining the temperature at 65 ° C. After 10 hours, the reaction was stopped by cooling the reactor with water to obtain a reaction solution. After cooling the reaction solution to room temperature, the unreacted monomer is purged, and the resulting reaction solution is filtered through diatomaceous earth to remove the solid matter to obtain a solid content concentration of 50% by mass and a number average molecular weight (M _n ) = 16000. And a solid fluorine-containing copolymer A having a mass average molecular weight (M _w ) = 50,000 and a hydroxyl value of 57 mgKOH / g was obtained.
The average number of moles of functional groups contained in the first functional group per mole of the resulting fluorinated copolymer A was 51 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 2)
In the same reactor as in Synthesis Example 1, 600 g of xylene, 200 g of EVE, 129 g of HBVE, 210 g of cyclohexyl vinyl ether (CHVE), 10 g of potassium carbonate and 3.5 g of PBPV are charged and solidified and degassed with liquid nitrogen. Dissolved oxygen in the liquid was removed.
Next, 660 g of CTFE was introduced, and the solid fluorine-containing copolymer B having a solid content of 50% by mass, M _n = 12000, M _w = 36000, and a hydroxyl value of 52 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer B was 34 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 3)
In the same reactor as in Synthesis Example 1, 590 g of xylene, 120 g of EVE, 254 g of HBVE, 200 g of CHVE, 11 g of potassium carbonate and 3.5 g of PBPV are charged and dissolved in liquid by solidification and degassing with liquid nitrogen. Oxygen was removed.
Next, 650 g of CTFE was introduced, and the solid fluorine-containing copolymer C having a solid content concentration of 50% by mass, M _n = 6000, M _w = 16000, and a hydroxyl value of 90 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer C was 26 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 4)
In the same reactor as in Synthesis Example 1, 580 g of xylene, 78 g of EVE, 251 g of HBVE, 273 g of CHVE, 11 g of potassium carbonate and 3.5 g of PBPV are charged and dissolved in liquid by solidification and degassing with liquid nitrogen. Oxygen was removed.
Subsequently, 640 g of CTFE was introduced, and the solid fluorine-containing copolymer D having a solid content of 50% by mass, M _n = 10000, M _w = 36000, and a hydroxyl value of 98 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer D was 63 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 5)
In the same reactor as Synthesis Example 1, 250 g of xylene, 530 g of t-butyl alcohol, 189 g of EVE, 123 g of HBVE, 200 g of CHVE, 11 g of potassium carbonate, and 2,2′-azobisisobutylnitrile as a polymerization initiator 0.5 g of (AIBN) was charged, and dissolved oxygen in the liquid was removed by solidification and degassing with liquid nitrogen.
Next, 620 g of CTFE was introduced, and the solid fluorine-containing copolymer E having a solid content concentration of 40% by mass, M _n = 40000, M _w = 100,000, and a hydroxyl value of 52 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer E was 94 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 6)
The same reactor as in Synthesis Example 1 was charged with 710 g of xylene, 133 g of HBVE, 520 g of CHVE, 11 g of potassium carbonate, and 3.5 g of PBPV, and the dissolved oxygen in the liquid was removed by solidification and degassing with liquid nitrogen.
Next, 620 g of CTFE was introduced, and then the solid fluorine-containing copolymer F having a solid content concentration of 50 mass%, M _n = 11000, M _w = 40000, and a hydroxyl value of 52 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer F was 37 moles of hydroxyl groups.

(Fluorine-containing copolymer synthesis example 7)
In the same reactor as in Synthesis Example 1, 720 g of xylene, 133 g of EVE, 126 g of HBVE, 320 g of CHVE, 11 g of potassium carbonate and 3.5 g of PBPV are charged and dissolved in liquid by solidification and degassing with liquid nitrogen. Oxygen was removed.
Next, 620 g of CTFE was introduced, and the solid fluorine-containing copolymer F having a solid content concentration of 50% by mass, M _n = 7000, M _w = 18000, and a hydroxyl value of 51 mgKOH / g was obtained in the same procedure as in Synthesis Example 1. It was.
The average number of moles of the functional groups in the obtained fluorinated copolymer G was 16 moles of hydroxyl groups.

(Laminated body production examples 1 to 7)
As a base material, a 200 μm-thick ETFE film (manufactured by Asahi Glass Co., Ltd., product name: Aflex) was subjected to corona discharge treatment at a discharge density of 200 W · min / m ² . The surface tension of the surface subjected to the discharge treatment was 0.045 N / m.
Using the fluorinated copolymers A to G obtained in Synthesis Examples 1 to 7, respectively, 100 parts by mass of the fluorinated copolymer and 20 parts by mass of the aluminum paste were dissolved in 20 parts by mass of the solvent to obtain gravure ink ( A non-curable coating film-forming composition) was prepared.
As the aluminum paste, Asahi Kasei Chemicals Corporation, trade name: HR7000, solid content concentration 50 mass% was used. As the solvent, a mixed solution in which toluene and methyl ethyl ketone were mixed at a mass ratio of 1: 1 was used.
Subsequently, the gravure plate engraved on 35 μm and 175 lines was filled with the gravure ink prepared above, and polka dot gravure printing was performed, followed by drying at 80 ° C. for 20 seconds to obtain a printed matter (laminate).

(Evaluation)
The following evaluation was implemented about the printed matter (laminated body) obtained by each of laminated body manufacture examples 1-7. The results are shown in Table 1 below.
(1) Initial adhesion The peeling test which affixes cello tape (trademark) on the printed gravure ink, and peels off rapidly was done. It was visually determined whether or not the ink was transferred to the cello tape side.

(2) Weather resistance test Using a metal halide lamp type accelerated weather resistance tester (trade name: die plastic metal weather, manufactured by Dainippon Plastic Co., Ltd.), after a 1000 hour test, the same peel test as in (1) Initial adhesion evaluation Went. It was visually determined whether or not the ink was transferred to the cello tape side.
(3) Moisture resistance test After exposure to a constant temperature and humidity tester at 85 ° C. and 85% humidity for 1000 hours, a peel test similar to the above (1) evaluation of initial adhesion was performed. It was visually determined whether or not the ink was transferred to the cello tape side.

In the production examples 1, 2, and 6 in which the mass average molecular weight of the fluorinated copolymer and the average number of functional group moles per mol of the copolymer are all within the scope of the present invention, good evaluation results were obtained in all tests. Obtained.

Claims (3)

The coating composition is formed by applying the following composition for forming a non-curable coating film on a part or all of the fluororesin substrate and drying it at 60 to 150 ° C. for 2 to 20 seconds. A method for producing a laminate.
Non-curable coating film-forming composition: comprising a fluorine-containing copolymer and a solvent, wherein the fluorine-containing copolymer has a mass average molecular weight (Mw) of 30,000 to 60,000, and the fluorine-containing copolymer polymers one mole per hydroxyl group, a carboxyl group, is less than an amide group and the first average number of moles of total functional groups contained in the functional groups is 33 or more 54 consisting of a glycidyl group, the average moles of said total The composition for non-hardening-type coating film formation whose ratio of the average mole number of the hydroxyl group per mole of the said fluorine-containing copolymer with respect to a number is 80% or more.   The manufacturing method of the laminated body of Claim 1 in which the said composition for non-hardening-type coating-film formation contains a coloring component.   The manufacturing method of the laminated body of Claim 1 or 2 by which the surface in which the said coating film is formed of the said fluororesin base | substrate is surface-treated before coating-film formation.