Resin Composition and Laminate

Abstract

A resin composition containing a copolymer having a fluoroolefin unit and a hydroxyl group-containing monomer unit, and an esterified cellulose resin, wherein the content of the esterified cellulose resin is 0.2 to 9 parts by mass relative to 100 parts by mass of the copolymer having a fluoroolefin unit and a hydroxyl group-containing monomer unit. A laminate includes a coating film formed from the resin composition.

Description

Technical Field

[0001] The present disclosure relates to a resin composition and a laminate. Background Art

[0002] Fluororesin films have excellent weather resistance and stain resistance, etc., and are therefore used as membrane materials (roof materials, outer wall materials, etc.) in membrane structure facilities (sports facilities (swimming pools, gymnasiums, tennis courts, football fields, track and field stadiums, etc.), warehouses, convention halls, exhibition halls, horticultural facilities (horticultural greenhouses, agricultural greenhouses, etc.)). However, since the fluororesin film has a high sunlight transmittance, when it is used as a membrane material for a membrane structure facility that is exposed to sunlight, there are cases where the inside of the membrane structure facility is too bright and the inside temperature of the membrane structure facility is too high. Therefore, by printing a coating on the fluororesin film, the sunlight reflectance can be increased. In addition, the team colors, logos, etc. of sports teams using the sports facilities can be printed on the membrane with the coating.

[0003] As a coating applicable to a fluororesin film, a coating containing a fluororesin having excellent weather resistance similar to that of the fluororesin film is preferably used. For example, Patent Document 1 proposes a non-curable coating film-forming composition for coating on a fluororesin substrate, which contains a fluororesin and a solvent, wherein the weight-average molecular weight of the above fluororesin is within a specific range and has a specific functional group in a specific ratio.

[0004] In addition, Patent Document 2 proposes a fluororesin coating containing a white pigment having a specific composition or a known green pigment, and a fluororesin film using the fluororesin coating.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Laid-Open No. 2006-152061

[0008] Patent Document 2: International Publication No. 2011 / 013572 Summary of the Invention

[0009] Technical Problem to be Solved by the Invention

[0010] In order to protect against abrasion caused by contact with rain, small stones, sand, etc., and friction with aggregates for fixing the membrane, most of the coating films formed by coating are arranged with the printing surfaces facing each other. In addition, sometimes two films with the printing surfaces facing each other are fabricated, transported to the site, unfolded, and inflated with air. When the coating films come into contact with each other, there is a problem of blocking.

[0011] On the other hand, since the film for membrane structures can be used as a membrane material for roofs, walls, etc. by itself, deformation caused by snow load, vibration caused by wind, and impact caused by raindrops, etc. often occur repeatedly. For the coating printed on such a film, high adhesion that does not peel off even when the film is deformed is required.

[0012] However, the methods described in Patent Documents 1 and 2 still have room for improvement in terms of achieving both adhesion and anti-blocking properties.

[0013] The present disclosure relates to providing a resin composition having excellent adhesion and anti-blocking properties, and a laminate having a coating film formed from the resin composition.

[0014] Technical solutions for solving the technical problems

[0015] The technical solutions for solving the above technical problems include the following forms.

[0016] <1> A resin composition containing a copolymer having a fluoroolefin unit and a hydroxyl group-containing monomer unit, and an esterified cellulose resin, wherein the content of the esterified cellulose resin is 0.2 to 9 parts by mass with respect to 100 parts by mass of the copolymer having a fluoroolefin unit and a hydroxyl group-containing monomer unit.

[0017] <2> The resin composition according to <1>, wherein the hydroxyl group content of the above esterified cellulose resin is 0.1 to 10% by mass.

[0018] <3> The resin composition according to <1> or <2>, wherein the above esterified cellulose resin includes at least one selected from cellulose acetate butyrate resin and cellulose acetate propionate resin.

[0019] <4> The resin composition according to any one of <1> to <3>, wherein the above fluoroolefin includes at least one selected from vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, and (perfluoroalkyl)ethylene.

[0020] <5> The resin composition according to any one of <1> to <4>, wherein the above hydroxyl group-containing monomer includes at least one selected from allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, (meth)acrylic acid hydroxyalkyl ester, hydroxyalkyl carboxylic acid vinyl ester, and hydroxyalkyl carboxylic acid allyl ester.

[0021] <6> The resin composition according to any one of <1> to <5>, wherein

[0022] it does not contain a curing agent; or

[0023] It contains a curing agent, and the molar ratio of the curable group in the above-mentioned curing agent to the hydroxyl group in the copolymer having a fluoroolefin unit and a monomer unit containing a hydroxyl group is 0.5 or less.

[0024] <7>The resin composition according to any one of <1> to <6> above, which is a coating applied to a substrate containing a fluororesin.

[0025] <8>A laminate comprising a substrate and a coating film formed from the resin composition according to any one of <1> to <6> above.

[0026] <9>The laminate according to <8> above, wherein the above-mentioned substrate contains a fluororesin.

[0027] <10>The laminate according to <9> above, wherein the above-mentioned fluororesin contains at least one selected from the group consisting of a vinyl fluoride polymer, a vinylidene fluoride polymer, a vinylidene fluoride - hexafluoropropylene copolymer, a tetrafluoroethylene - hexafluoropropylene - vinylidene fluoride copolymer, a tetrafluoroethylene - propylene copolymer, a tetrafluoroethylene - vinylidene fluoride - propylene copolymer, an ethylene - tetrafluoroethylene copolymer, a hexafluoropropylene - tetrafluoroethylene copolymer, an ethylene - hexafluoropropylene - tetrafluoroethylene copolymer, a perfluoro(alkyl vinyl ether) - tetrafluoroethylene copolymer, a chlorotrifluoroethylene polymer, and an ethylene - chlorotrifluoroethylene copolymer.

[0028] <11>The laminate according to any one of <8> to <10> above, wherein the laminate is a film material for a membrane structure facility, a screen, a billboard, or solar light control.

[0029] Advantages of the Invention

[0030] According to the present disclosure, a resin composition having excellent adhesion and anti - sticking properties, and a laminate having a coating film formed from the resin composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a cross - sectional view showing an example of the laminate in one aspect of the present disclosure.

[0032] Figure 2 It is a cross - sectional view showing another example of the laminate in one aspect of the present disclosure. DETAILED DESCRIPTION

[0033] Hereinafter, the embodiments of the present disclosure will be described in detail, but the embodiments of the present disclosure are not limited to the following embodiments.

[0034] In the present disclosure, the term "process" includes a process independent of other processes, and also includes the process when it can achieve the purpose of this process even if it cannot be clearly distinguished from other processes.

[0035] In the present disclosure, the numerical range represented by "~" includes the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0036] In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, if not particularly limited, the content ratio or content of each component represents the total content ratio or total amount of the plurality of substances present in the composition.

[0037] In the present disclosure, when describing the embodiments with reference to the drawings, the configuration of the embodiments is not limited to the configuration shown in the drawings. In addition, the dimensions of the components in each drawing are conceptual, and the relative relationship of the dimensions between the components is not limited thereto. In addition, in each drawing, components having substantially the same function are denoted by the same reference numerals throughout the drawings, and repeated descriptions may sometimes be omitted.

[0038] In the present disclosure, a "unit" means a part derived from a monomer that exists in a polymer and constitutes the polymer. In addition, a structure obtained by chemically converting the structure of a certain unit after forming the polymer is also called a unit. Additionally, depending on the circumstances, the unit derived from each monomer is described by adding the name of the monomer and "unit".

[0039] In the present disclosure, films and sheets are collectively referred to as "films" regardless of their thickness.

[0040] In the present disclosure, acrylate and methacrylate are collectively referred to as "(meth)acrylate".

[0041] 《Resin Composition》

[0042] The resin composition of the present disclosure contains a copolymer having a fluoroolefin unit and a monomer unit containing a hydroxyl group (hereinafter also referred to as "specific fluororesin") and an esterified cellulose resin, and the content of the above esterified cellulose resin is 0.2 to 9 parts by mass with respect to 100 parts by mass of the copolymer having a fluoroolefin unit and a monomer unit containing a hydroxyl group. The resin composition of the present disclosure can achieve both excellent adhesion to the substrate and anti-blocking properties.

[0043] Generally, an esterified cellulose resin is adhered to a PET film, a polystyrene film, etc. that have been subjected to surface treatment by corona discharge, plasma discharge, etc. However, for a fluororesin film, it is difficult to adhere even when surface treatment is performed by the same method. In addition, the fluororesin and the esterified cellulose resin cannot be compatible in any proportion and are not easily entangled with each other. Therefore, in a resin composition containing a fluororesin for imparting a fluororesin film, it is generally considered difficult to apply an esterified cellulose resin. However, when only a small amount of an esterified cellulose resin is blended in a specific fluororesin, the anti-blocking property can be significantly improved, and the adhesion to the fluororesin film can also be maintained. In particular, when only 0.2 parts by mass of an esterified cellulose resin is blended with respect to 100 parts by mass of a specific fluororesin, an increase in the blocking temperature can be observed. As the reason, it is considered that when the applied resin composition dries, the esterified cellulose resin having a high glass transition temperature is concentrated in the surface layer of the resin composition in contact with the external atmosphere.

[0044] Hereinafter, each component of the resin composition will be described in detail.

[0045] <Specific fluororesin>

[0046] The resin composition contains a copolymer having a fluoroolefin unit and a hydroxyl group-containing monomer unit (i.e., a specific fluororesin). Since the specific fluororesin has a hydroxyl group-containing monomer unit in addition to the fluoroolefin unit, it has good adhesion to a substrate in addition to properties of a fluororesin such as weather resistance and stain resistance. The specific fluororesin may have other monomer units in addition to the fluoroolefin unit and the hydroxyl group-containing monomer unit, or may not have other monomer units. The specific fluororesin may be used alone or in combination of two or more.

[0047] As the fluoroolefin, a fluoroolefin having 10 or less carbon atoms is preferable. Specific examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene (hereinafter also referred to as "CTFE"), tetrafluoroethylene (hereinafter also referred to as "TFE"), hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, (perfluoroalkyl)ethylene, etc.

[0048] In addition, (perfluoroalkyl)ethylene is a fluoroolefin represented by CH 2 =CH-Rf (wherein Rf represents a perfluoroalkyl group). Specifically, examples include (perfluoromethyl)ethylene, (perfluorobutyl)ethylene, etc.

[0049] As the (perfluoroalkyl)ethylene, a (perfluoroalkyl)ethylene having 3 to 8 carbon atoms is preferable. The perfluoroalkyl group may be linear or branched.

[0050] As the fluoroolefin other than (perfluoroalkyl)ethylene, a fluoroolefin having 2 or 3 carbon atoms is preferable.

[0051] The hydroxyl group-containing monomer in the hydroxyl group-containing monomer unit may be a monomer having a fluorine atom or a monomer not having a fluorine atom, and a monomer not having a fluorine atom is preferred. Examples of the hydroxyl group-containing monomer include allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, (meth)acrylic acid hydroxyalkyl ester, vinyl hydroxyalkyl carboxylate, allyl hydroxyalkyl carboxylate, etc. In the monomer having a hydroxyalkyl group, the alkyl group of the hydroxyalkyl group may be any of linear, branched, and cyclic, or a combination thereof. Further, when the alkyl group is a combination of two or more of these, the hydroxyl group may be disposed at any position. The hydroxyalkyl group of the above-mentioned monomer having a hydroxyalkyl group may be a hydroxycycloalkyl group, a cycloalkyl group substituted with a hydroxyalkyl group, etc. The carbon number of the hydroxyalkyl group is preferably 10 or less, more preferably 6 or less.

[0052] Examples of the hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, etc.

[0053] Examples of the hydroxyalkyl allyl ether include 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 4-hydroxycyclohexyl allyl ether, etc.

[0054] Examples of the (meth)acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth)acrylate, etc.

[0055] Examples of the vinyl hydroxyalkyl carboxylate include vinyl glycolate, vinyl hydroxyisobutyrate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxypentanoate, vinyl hydroxycyclohexanecarboxylate, etc.

[0056] Examples of the allyl hydroxyalkyl carboxylate include allyl glycolate, allyl hydroxypropionate, allyl hydroxybutyrate, allyl hydroxyisobutyrate, allyl hydroxycyclohexanecarboxylate, etc.

[0057] Examples of the monomer unit other than the fluoroolefin unit and the hydroxyl group-containing monomer unit include a unit derived from a fluorine-containing monomer other than a fluoroolefin, a unit derived from a monomer not having a fluorine atom, etc.

[0058] Examples of the fluorine-containing monomer other than a fluoroolefin include perfluoro(alkyl vinyl ether), perfluoro unsaturated cyclic ether, etc.

[0059] As the perfluoro(alkyl vinyl ether), a perfluoro(alkyl vinyl ether) having a carbon number of 10 or less is preferred, and more preferably its carbon number is 6 or less. Specifically, examples thereof include perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), perfluoro(heptyl vinyl ether), etc.

[0060] Examples of monomers without fluorine atoms include olefins, vinyl ethers, allyl ethers, vinyl carboxylates, allyl carboxylates, unsaturated carboxylates, etc. Among them, except for olefins, the carbon number of the above monomers is preferably 16 or less, more preferably 12 or less.

[0061] As olefins, olefins with 2 to 4 carbon atoms are preferred, and examples include ethylene, propylene, isobutene, etc.

[0062] Examples of vinyl ethers include cycloalkyl vinyl ethers (such as cyclohexyl vinyl ether), alkyl vinyl ethers (such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, etc.).

[0063] Examples of allyl ethers include alkyl allyl ethers (such as ethyl allyl ether, hexyl allyl ether, etc.).

[0064] Examples of vinyl carboxylates include vinyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid, etc.). In addition, as vinyl esters of carboxylic acids having branched alkyl groups, those such as Veova 9 (registered trademark) and Veova 10 (registered trademark) manufactured by Shell Chemical Company can also be used.

[0065] Examples of allyl carboxylates include allyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid, etc.).

[0066] Examples of unsaturated carboxylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.

[0067] In addition, the specific fluororesin may further contain monomer units having crosslinkable groups other than hydroxyl groups such as carboxyl groups, amide groups, epoxy groups, etc.

[0068] As a combination of fluorine olefin units and monomer units containing hydroxyl groups in the specific fluororesin, a combination of at least one selected from tetrafluoroethylene and chlorotrifluoroethylene and hydroxyalkyl vinyl ether is particularly preferred.

[0069] The proportion of fluorine olefin units in all units of the specific fluororesin is preferably 30 to 70 mol%, more preferably 40 to 60 mol%. If the proportion of fluorine olefin units is above the lower limit value of the above range, it tends to obtain a coating film with excellent weather resistance, stain resistance, etc. If the proportion of fluorine olefin units is below the upper limit value of the above range, the adhesion between the substrate and the coating film tends to be more excellent.

[0070] The proportion of the hydroxy group-containing monomer unit in the specific fluororesin in all the units of the specific fluororesin is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%. If the proportion of the hydroxy group-containing monomer unit is above the lower limit value of the above range, the adhesion between the coating film and the substrate tends to be more excellent. If the proportion of the hydroxy group-containing monomer unit is below the upper limit value of the above range, the flexibility of the coating film tends to be excellent.

[0071] The proportion of the monomer unit in the fluororesin can be confirmed by a nuclear magnetic resonance apparatus (NMR).

[0072] In one form, as the specific fluororesin, a copolymer containing a fluoroolefin unit, a hydroxy group-containing monomer unit, and a non-fluorine monomer unit without a hydroxy group is preferred. Hereinafter, this copolymer is also referred to as "copolymer (A)".

[0073] As the combination of the monomers constituting the copolymer (A), considering the points that the solar reflectance of the coating film is not easily reduced for a long time when the resin composition is used for forming a solar reflective layer, the excellent adhesion between the coating film and the substrate, and the excellent flexibility of the coating film, the following combination (1) is preferred, and the following combination (2) or (3) is more preferred.

[0074] Combination (1)

[0075] · Fluoroolefin: Tetrafluoroethylene or chlorotrifluoroethylene

[0076] · Hydroxy group-containing monomer: Hydroxyalkyl vinyl ether

[0077] · Non-fluorine monomer without a hydroxy group: At least one selected from cycloalkyl vinyl ether, alkyl vinyl ether, and vinyl carboxylate

[0078] Combination (2)

[0079] · Fluoroolefin: Tetrafluoroethylene

[0080] · Hydroxy group-containing monomer: Hydroxyalkyl vinyl ether

[0081] · Non-fluorine monomer without a hydroxy group: At least one selected from tert-butyl vinyl ether and vinyl carboxylate

[0082] Combination (3)

[0083] · Fluoroolefin: Chlorotrifluoroethylene

[0084] · Hydroxy group-containing monomer: Hydroxyalkyl vinyl ether

[0085] · Non-fluorine monomer without a hydroxy group: At least one selected from tert-butyl vinyl ether and vinyl carboxylate

[0086] The proportion of the fluoroolefin unit in the copolymer (A) in all the units (100 mol%) of the copolymer (A) is preferably 30 to 70 mol%, more preferably 40 to 60 mol%. If the proportion of the fluoroolefin unit is above the lower limit value of the above range, a coating film excellent in weather resistance, stain resistance, etc. tends to be obtained. If the proportion of the fluoroolefin unit is below the upper limit value of the above range, the adhesion between the substrate and the coating film tends to be more excellent.

[0087] The proportion of the hydroxy group-containing monomer unit in the copolymer (A) in all the units of the copolymer (A) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%. If the proportion of the hydroxy group-containing monomer unit is above the lower limit value of the above range, the adhesion between the coating film and the substrate tends to be more excellent. If the proportion of the hydroxy group-containing monomer unit is below the upper limit value of the above range, the flexibility of the coating film tends to be excellent.

[0088] The proportion of the non-fluorinated monomer unit without a hydroxy group in the copolymer (A) in all the units of the copolymer (A) is preferably 20 to 60 mol%, more preferably 30 to 50 mol%. If the proportion of this monomer unit is above the lower limit value of the above range, the flexibility of the coating film tends to be excellent. If the proportion of this monomer unit is below the upper limit value of the above range, the adhesion between the coating film and the substrate tends to be more excellent.

[0089] Examples of commercially available products of the copolymer (A) include the LUMIFLON (registered trademark) series (LF200, LF100, LF710, LF600, etc.) (manufactured by AGC Inc.), the ZEFFLE (registered trademark) GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) (manufactured by Daikin Industries, Ltd.), the FLOANATE (registered trademark) series (K-700, K-702, K-703, K-704, K-705, K-707, etc.) (manufactured by DIC Corporation), the ETERFLON series (4101, 41011, 4102, 41021, 4261A, 4262A, 42631, 4102A, 41041, 41111, 4261A, etc.) (manufactured by Eternal Chemical Co., Ltd.), etc.

[0090] From the viewpoint of obtaining good adhesion, the hydroxyl value of the specific fluororesin is preferably 10 to 150 mgKOH / g, more preferably 15 to 120 mgKOH / g, still more preferably 20 to 100 mgKOH / g, and particularly preferably 20 to 50 mgKOH / g. The hydroxyl value of the fluororesin is the value measured according to Method A of ISO 14900:2001.

[0091] The content rate of the specific fluororesin in the resin composition can be 30% by mass or more, can be 40% by mass or more, and can be 50% by mass or more with respect to the total mass of the resin composition. In addition, the content rate of the specific fluororesin in the resin composition can be 90% by mass or less, and can be 80% by mass or less with respect to the total mass of the resin composition. From this viewpoint, the content rate of the specific fluororesin in the resin composition can be 30 to 90% by mass, can be 40 to 80% by mass, or can be 50 to 80% by mass.

[0092] <Esterified cellulose resin>

[0093] The resin composition of the present disclosure contains an esterified cellulose resin, and the content of the esterified cellulose resin is 0.2 to 9 parts by mass with respect to 100 parts by mass of the specific fluororesin. By making the content of the esterified cellulose resin with respect to the specific fluororesin within the above range, good adhesion and anti-blocking properties can be achieved at the same time. In addition, as described above, generally, since the compatibility of the esterified cellulose resin with the fluororesin is not high, the cohesion tends to decrease when mixed with the fluororesin. However, in the resin composition of the present disclosure, if the content of the esterified cellulose resin is within the above range, the decrease in the cohesion of the coating film can be suppressed.

[0094] The content of the esterified cellulose resin is 0.2 to 9 parts by mass, preferably 0.5 to 7 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the specific fluororesin. If the content of the esterified cellulose resin is above the lower limit value of the above range, good anti-blocking properties can be obtained, and if it is below the upper limit value of the above range, the adhesion of the resin composition to the fluororesin substrate after the weather resistance test is particularly excellent.

[0095] From the same viewpoint, the content of the esterified cellulose resin is preferably 0.20 to 9.00 parts by mass, more preferably 0.50 to 7.00 parts by mass, and further preferably 1.00 to 5.00 parts by mass with respect to 100 parts by mass of the specific fluororesin.

[0096] The masses of the specific fluororesin and the esterified cellulose resin in the resin composition are quantified by utilizing the difference in solubility. For example, by dissolving the specific fluororesin in a solvent (such as toluene) that does not dissolve the esterified cellulose resin but dissolves the specific fluororesin, the masses of the respective components can be obtained and the mass ratio can be calculated. In addition, by measuring infrared spectroscopy, the presence and amount of the esterified cellulose resin present in the resin composition can be confirmed.

[0097] In addition, from the viewpoint of anti-blocking property, the content of the esterified cellulose resin is preferably 1 part by mass or more, may be 2 parts by mass or more, or may be 3 parts by mass or more with respect to 100 parts by mass of the specific fluororesin. Before the content of the esterified cellulose resin reaches about 5 parts by mass with respect to 100 parts by mass of the specific fluororesin, the blocking temperature tends to increase as the amount increases. On the other hand, even if the amount of the esterified cellulose resin is increased after exceeding 5 parts by mass, the blocking temperature can be maintained but will not increase further. Therefore, from the viewpoint of excellent adhesion to the substrate, cohesion of the coating film, etc., the content of the esterified cellulose resin may be 8 parts by mass or less, may be 7 parts by mass or less, may be 6 parts by mass or less, or may be 5 parts by mass or less with respect to 100 parts by mass of the specific fluororesin.

[0098] From the same viewpoint, the content of the esterified cellulose resin is preferably 1.00 part by mass or more, may be 2.00 parts by mass or more, or may be 3.00 parts by mass or more with respect to 100 parts by mass of the specific fluororesin. In addition, the content of the esterified cellulose resin may be 8.00 parts by mass or less, may be 7.00 parts by mass or less, may be 6.00 parts by mass or less, or may be 5.00 parts by mass or less with respect to 100 parts by mass of the specific fluororesin.

[0099] Examples of the esterified cellulose resin include cellulose acetate resin, cellulose acetate butyrate (CAB) resin, cellulose acetate propionate (CAP) resin, etc. Generally, CAP can be obtained by hydrolyzing cellulose after tritertiary esterification with acetic acid and propionic acid. In addition, CAB can be obtained by hydrolyzing cellulose after tritertiary esterification with acetic acid and butyric acid.

[0100] The esterified cellulose resin is preferably at least one selected from CAB and CAP. The esterified cellulose resin can be used alone or in combination of two or more.

[0101] The properties of the esterified cellulose resin can be represented by molecular weight, glass transition temperature, hydroxyl group content, acetyl group content, butyryl group content, propionyl group content, etc.

[0102] The hydroxyl content of the esterified cellulose resin is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass. If the hydroxyl content is within the above range, it is considered to be relatively easy to fuse with the fluororesin and to properly maintain the cohesive force when the coating is made. If the hydroxyl content of the esterified cellulose resin is below the upper limit of the above range, the water absorption of the coating formed by the resin composition is suppressed, and good weather resistance can be obtained. In particular, it is useful in that even when the resin composition does not contain a curing agent or the content of the curing agent is suppressed, good weather resistance can be obtained. In addition, when the amount of water in the coating is suppressed, the photodecomposition of the fluororesin is suppressed, thereby suppressing the reduction in the adhesion of the coating. In particular, it is useful in that, when using pigments such as aluminum pigments and titanium oxide, the adhesion is easily reduced due to photodecomposition, but even when these pigments are used, the reduction in adhesion can be suppressed.

[0103] When the esterified cellulose resin is CAB, the acetyl content in CAB is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. In addition, the butyryl content in CAB is preferably 10 to 60% by mass, more preferably 20 to 55% by mass. When the butyryl content is high, the solubility in organic solvents is excellent.

[0104] When the esterified cellulose resin is CAP, the acetyl content in CAP is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. In addition, the propionyl content in CAP is preferably 30 to 60% by mass, more preferably 40 to 50% by mass. When the propynyl content is high, the solubility in organic solvents is excellent.

[0105] The hydroxyl content, acetyl content, butyryl content and propionyl content of the esterified cellulose resin are values ​​obtained according to ASTM D817-12 (2019): Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate.

[0106] The number-average molecular weight of the esterified cellulose resin is preferably from 12,000 to 75,000, more preferably from 20,000 to 50,000. If the number-average molecular weight is above the lower limit of the above range, the addition effect of cellulose can be better exerted, and if it is below the upper limit of the above range, a resin composition with excellent gravure printability viscosity can be obtained. The number-average molecular weight of the esterified cellulose resin can be measured by gel permeation chromatography (GPC). Specifically, using tetrahydrofuran, it is measured in terms of polystyrene with a gel permeation chromatography device (GPC device: manufactured by Tosoh Corporation, HLC-8320GPC, chromatographic column: TSKgel α-M).

[0107] From the viewpoint of further improving the anti-blocking property, the glass transition temperature of the esterified cellulose resin is preferably 80 °C or higher, more preferably 100 °C or higher, and still more preferably 120 °C or higher. The upper limit of the above glass transition temperature is not particularly limited. For example, the above glass transition temperature can be 200 °C or lower.

[0108] The glass transition temperature of the esterified cellulose resin is a value measured by the dynamic viscoelasticity measurement (DMA) method.

[0109] Examples of commercially available esterified cellulose resins include CAP-482-20, CAP-482-0.5, CAP-504-0.2, CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1, CAB-500-5, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-381-20, CAB-381-20 BP, CAB-321-0.1, CAB-171-15 (all are trade names) manufactured by Eastman Chemical Japan Co., Ltd., etc. Among them, CAB-381-2 and CAB-551-0.01 are preferred.

[0110] <Curing agent>

[0111] The resin composition of the present disclosure may contain a curing agent or may not contain a curing agent. If the resin composition contains a curing agent, improvements in water resistance, solvent resistance, and anti-blocking properties are likely to be seen. In particular, if a curing agent is blended, the blocking temperature tends to further increase. On the other hand, from the viewpoint of adhesion to the fluororesin substrate, it is preferred that the resin composition does not contain a curing agent or, if it contains one, contains only a small amount. In addition, in applications such as film structures, when joining substrates to each other by hot pressing or the like, it is sometimes necessary to remove the coating film applied to the substrate. The coating film can be physically removed using a sandblaster, a grinder, etc., but in the case of removing the coating film with a solvent, the coating film that has undergone a chemical curing reaction due to the use of a curing agent is sometimes not easily removed. Therefore, from the viewpoint of easy removability, it is preferred to control the content of the curing agent. According to the resin composition of the present disclosure, excellent anti-blocking properties can be obtained even when the content of the curing agent is small.

[0112] As the curing agent, a curing agent known as a curing agent for coatings can be appropriately used. Specifically, examples include isocyanate curing agents, blocked isocyanate curing agents, aminoplast curing agents, polycarboxylic acid curing agents, polyamine curing agents, etc. The selection of the curing agent is preferably considered in view of the type of curing reactive sites of the fluororesin and the curing characteristics. As the curing agent used in combination with a specific fluororesin, an isocyanate curing agent, a blocked isocyanate curing agent, or an aminoplast curing agent is preferred. The curing agent can be used alone or in combination of two or more.

[0113] From the above viewpoints, it is preferred that the resin composition does not contain a curing agent or, if it contains a curing agent, the molar ratio of the curable groups in the curing agent to the hydroxyl groups in the specific fluororesin (i.e., the number of moles of the curable groups in the curing agent / the number of moles of the hydroxyl groups in the specific fluororesin) is 1.0 or less, more preferably 0.5 or less, and still more preferably 0.4 or less. The above molar ratio can be 0.3 or less or can be 0.2 or less. From the viewpoint of excellent water resistance, solvent resistance, and anti-blocking properties, when a curing agent is blended, the above molar ratio is preferably 0.05 or more. Here, the curable group refers to a functional group that undergoes a curing reaction with the hydroxyl groups in the specific fluororesin.

[0114] For example, when assuming a curing agent containing an isocyanate group as the curing agent, it is preferred that the resin composition does not contain a curing agent containing an isocyanate group or the molar ratio of the isocyanate groups in the curing agent containing an isocyanate group in the resin composition to the hydroxyl groups in the specific fluororesin ([NCO] / [OH]) is in the above range.

[0115] In the case of using a curing agent that undergoes a curing reaction at 25°C, it is preferable to prepare a two-component curable resin composition, in which a main agent containing a specific fluororesin and a curing agent are separately prepared in advance and mixed when forming a coating film. It is preferable that the main agent contains other components that do not react with the specific fluororesin. In the case of using a two-component curable resin composition, a coating film is formed on the substrate by applying the resin composition in which the main agent and the curing agent are mixed onto the substrate and drying it at room temperature.

[0116] In addition, in the case of using a curing agent that undergoes a curing reaction by heating, a one-component curable resin composition in which the curing agent and the specific fluororesin coexist in the resin composition can be prepared. In this case, a coating film is formed on the substrate by applying the resin composition onto the substrate and sintering it.

[0117] Examples of the curing agent that undergoes a curing reaction at 25°C include non-yellowing diisocyanates (hexamethylene diisocyanate, isophorone diisocyanate, etc.), polyisocyanate curing agents (adducts or polymers of the above non-yellowing diisocyanates, etc.).

[0118] Examples of the curing agent that undergoes a curing reaction by heating include blocked isocyanate curing agents, aminoplast curing agents, etc.

[0119] Polyisocyanate curing agents containing isocyanate groups are sometimes particularly useful. In this case, it is preferable to further add a curing catalyst such as dibutyltin dilaurate to promote curing.

[0120] <Other components>

[0121] The resin composition of the present disclosure may further contain components other than the above components. For example, the resin composition may contain resins other than the specific fluororesin and the esterified cellulose resin, and may contain various additives such as pigments, ultraviolet absorbers, near-infrared absorbing pigments, near-infrared reflecting pigments, adhesion improvers, and lubricants. These components can be used alone or in combination of two or more.

[0122] (Resins other than the specific fluororesin and the esterified cellulose resin)

[0123] Examples of the resins other than the specific fluororesin and the esterified cellulose resin include polyester resins, acrylic resins, epoxy resins, fluororesins other than the specific fluororesin, etc. Examples of the fluororesin other than the specific fluororesin include tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (hereinafter also referred to as "THV"), vinyl fluoride-vinyl ester copolymer, polytetrafluoroethylene (hereinafter also referred to as "PTFE"), etc.

[0124] When the resin composition contains a resin other than a specific fluororesin and an esterified cellulose resin, the content of the resin is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less with respect to the total mass of the resins in the resin composition. In addition, when referring to the content or content ratio of the resin, in the case where the component used as an additive is a resin, the above content or content ratio also includes the content or content ratio of the resin used as an additive.

[0125] (Pigment)

[0126] The resin composition of the present disclosure may contain coloring pigments such as organic pigments and inorganic pigments. Examples of the pigment include carbon black as a black pigment, iron oxide as a red pigment, aluminum cobalt oxide as a blue pigment, copper phthalocyanine as a blue pigment or a green pigment, perylene as a red pigment, and bismuth vanadate as a yellow pigment.

[0127] In order to adjust the visible light reflectance and the sunlight reflectance, the resin composition of the present disclosure may contain an aluminum-based pigment. For example, aluminum particles such as aluminum flakes, or aluminum particles coated with an organic substance or an inorganic substance on the surface (surface-treated aluminum particles) can be cited.

[0128] Examples of the organic substance in the surface-treated aluminum particles include resins, fatty acids, and silane coupling agents, and examples of the inorganic substance include inorganic oxides such as silica and metals other than aluminum. Among them, from the viewpoint that the visible light reflectance and the sunlight reflectance are not easily reduced in the long term, aluminum particles coated with an acrylic resin or silica are particularly preferred. Aluminum particles coated with an acrylic resin or silica are also referred to as "specific aluminum composite particles" hereinafter.

[0129] The total coating amount of the acrylic resin and silica in the specific aluminum composite particles is preferably 3 to 30 parts by mass, more preferably 3 to 25 parts by mass, and further preferably 4 to 20 parts by mass with respect to 100 parts by mass of the aluminum particles. If the total coating amount of the acrylic resin and silica is above the lower limit value of the above range, the aluminum particles can be sufficiently protected by the acrylic resin or silica, so the sunlight reflectance after forming a coating film is not easily reduced in the long term. If the total coating amount of the acrylic resin and silica is below the upper limit value of the above range, the dissolution of the aluminum particles due to the deterioration of the acrylic resin, or the generation of cracks inside the silica during the weather resistance test and the dissolution of the aluminum particles caused by the permeating moisture tend to be suppressed. In addition, as a result, the sunlight reflectance is not easily reduced in the long term.

[0130] When the resin composition contains specific aluminum complex particles, from the viewpoint of the balance among the solar reflectance, the viscosity of the resin composition, the adhesiveness, etc., the content of the specific aluminum complex particles is preferably 10 to 35% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass relative to the total mass of the resin composition.

[0131] The content of the pigment in the resin composition is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass relative to 100 parts by mass of the total amount of the resin in the resin composition. In addition, when referring to the content or the content ratio of the pigment, the above content or content ratio means the content or content ratio including the content or content ratio of the near-infrared absorbing pigment, the near-infrared reflecting pigment, etc. described later.

[0132] (UV absorber)

[0133] Examples of the UV absorber include inorganic UV absorbers, organic UV absorbers, etc.

[0134] Examples of the inorganic UV absorber include inorganic particles such as zinc oxide, titanium oxide, cerium oxide, iron oxide; inorganic composite particles formed by coating the surface of the above inorganic particles with inorganic substances such as silicon oxide, aluminum oxide, zirconium oxide, etc.

[0135] Examples of the organic UV absorber include triazine-based UV absorbers, benzophenone-based UV absorbers, etc., and triazine-based UV absorbers are preferred. Among them, 2-(2-hydroxy-4-[1-octyloxycarbonyloxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN 479), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN 460), 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyloxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (manufactured by BASF Japan Co., Ltd., trade name: TINUVIN 405) and other hydroxyphenyltriazine-based UV absorbers are preferred.

[0136] (Near-infrared absorbing pigment and near-infrared reflecting pigment)

[0137] Examples of the near-infrared absorbing pigment or near-infrared reflecting pigment include boron compounds such as lanthanum hexaboride as a green pigment, tungsten compounds such as cesium tungstate as a blue pigment, indium tin oxide as a light blue pigment, antimony tin oxide as a blue pigment, etc.

[0138] (Adhesion improver)

[0139] As the adhesion modifier (except for esterified cellulose resin), examples include silicon compounds, chlorinated polyethylene, acrylic resin beads, etc. The content of the adhesion improver (except for esterified cellulose resin) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

[0140] (Lubricant)

[0141] As the lubricant, examples include various waxes such as polyolefin waxes such as polyethylene wax, fatty acid amides, fatty acid esters, paraffin wax, polytetrafluoroethylene (PTFE) wax, carnauba wax, etc.

[0142] (Other additives)

[0143] The resin composition of the present disclosure may contain, as needed, additives such as anti-settling agents, plasticizers, dispersion stabilizers, filler materials, antioxidants, antistatic agents, matting agents (such as silica, alumina, etc.), adhesion improvers (such as silane coupling agents, etc.) in addition to the above.

[0144] (Solvent)

[0145] From the viewpoint of excellent coating properties, the resin composition of the present disclosure can be used by adding a solvent. The solvent only needs to be able to dissolve or disperse the specific fluororesin, and can be appropriately selected according to the coating method, considering the repellency of the coating on the substrate, the transfer rate, the drying property, the storage stability, etc.

[0146] Examples of the solvent include aqueous solvents, organic solvents, etc., and one kind can be used alone, or two or more kinds can be used in combination.

[0147] Examples of the organic solvent include toluene, xylene, ethylbenzene, methyl ethyl ketone, ethyl acetate, etc.

[0148] In gravure printing, in order to reduce printing defects such as coating unevenness and bleeding (Japanese: にじみ), a solvent with a Zahn cup viscosity of 15 to 30 seconds for the coating is preferably used.

[0149] In the case of inkjet, a high-boiling solvent can be added so that the ejection port of the coating does not dry out.

[0150] When the resin composition contains a solvent, the content of the solvent is preferably 30 to 90% by mass, more preferably 40 to 80% by mass with respect to the total mass of the resin composition (including the solvent). The content of the components other than the solvent in the resin composition is preferably 10 to 70% by mass, more preferably 20 to 60% by mass with respect to the total mass of the resin composition (including the solvent).

[0151] In addition, in the present disclosure, when referring to the content or content ratio of each component other than the solvent in the resin composition, in the case where the resin composition contains a solvent, the above content or content ratio refers to the content or content ratio in the resin composition excluding the solvent.

[0152] The resin composition preferably has a Zahn cup No. 3 viscosity of 15 to 30 seconds.

[0153] 〔Use of the resin composition〕

[0154] The resin composition of the present disclosure is suitable for use as a coating. In particular, the useful aspect of the resin composition of the present disclosure is that when used as a coating to coat a substrate containing a fluororesin, while taking into account properties such as weather resistance, it is also possible to take into account adhesion and anti-blocking properties. The details of the substrate containing the fluororesin will be described later.

[0155] 《Laminate》

[0156] The laminate of the present disclosure includes a substrate and a coating film formed from the above resin composition of the present disclosure. Hereinafter, specific examples of the laminate will be described with reference to the drawings.

[0157] Figure 1 It is a cross-sectional view showing an example of the laminate in one aspect of the present disclosure. The laminate 10 has a substrate 12 and a coating film 14 formed on the surface of the substrate 12 on the sunlight L incident side, and is a so-called top surface printed laminate.

[0158] Figure 2 It is a cross-sectional view showing another example of the laminate in one aspect of the present disclosure. The laminate 10 has a substrate 12 and a coating film 14 formed on the surface of the substrate 12 on the side opposite to the sunlight L incident side, and is a so-called back surface printed laminate.

[0159] In Figure 1 and 2 , the coating film 14 is only formed on one surface of the substrate 12, but the coating film 14 can also be formed on both surfaces of the substrate 12.

[0160] As Figure 1 and Figure 2 shown, the coating film 14 can be formed on the entire surface of the substrate 12 or on a part of the substrate 12.

[0161] <Substrate>

[0162] (Fluororesin)

[0163] The substrate contains a fluororesin. The fluororesin contained in the substrate is preferably a homopolymer or copolymer of a fluoroolefin. As the fluoroolefin, the fluoroolefins described above as the constituent units of the specific fluororesin can be exemplified. The fluororesin can be used alone or in combination of two or more.

[0164] Examples of the fluoroolefin copolymer include copolymers of two or more fluoroolefins, copolymers of one or more fluoroolefins and one or more olefins or perfluoro(alkyl vinyl ethers), etc. The number of carbon atoms of the fluoroolefin and the olefin is preferably 2 or 3. The number of carbon atoms of the perfluoro(alkyl vinyl ether) is preferably 3 to 6.

[0165] Examples of the preferred fluororesin include vinyl fluoride polymers (hereinafter also referred to as "PVF"), vinylidene fluoride polymers (hereinafter also referred to as "PVDF"), vinylidene fluoride - hexafluoropropylene copolymers, THV, tetrafluoroethylene - propylene copolymers, tetrafluoroethylene - vinylidene fluoride - propylene copolymers, ethylene - tetrafluoroethylene copolymers (hereinafter also referred to as "ETFE"), hexafluoropropylene - tetrafluoroethylene copolymers (hereinafter also referred to as "FEP"), ethylene - hexafluoropropylene - tetrafluoroethylene copolymers (hereinafter also referred to as "EFEP"), perfluoro(alkyl vinyl ether) - tetrafluoroethylene copolymers (hereinafter also referred to as "PFA"), chlorotrifluoroethylene polymers (hereinafter also referred to as "PCTFE"), and ethylene - chlorotrifluoroethylene copolymers (hereinafter also referred to as "ECTFE"). As the fluororesin, ETFE is particularly preferred.

[0166] The fluorine atom content in the fluororesin of the substrate is preferably 45% by mass or more, more preferably 50% by mass or more, and further preferably 55% by mass or more. If the fluorine atom content is above the lower limit value of the above range, the weather resistance, stain resistance, chemical resistance, and non - adhesion of the substrate are more excellent, especially the non - adhesion and stain resistance are excellent. The fluorine atom content can be determined by the method of combining a fluoride ion - selective electrode with gas chromatography after combustion.

[0167] The fluororesin contained in the substrate is preferably a fluororesin that can form a film. As the fluororesin contained in the substrate, a polymer with excellent weather resistance and a stress corresponding to 10% elongation of 10 MPa or more is preferred. The stress value corresponding to 10% elongation is determined by the method specified in JIS K7127:1999 (Plastics - Test methods for tensile properties - Part 3: Test conditions for films and sheets). Using dumbbell 5 as the test piece, it is calculated by dividing the tension when elongated at a tensile speed of 200 mm / minute by the initial cross - sectional area of the film. The stress corresponding to 10% elongation does not depend on the film thickness and depends largely on the composition of the fluororesin. If the stress corresponding to 10% elongation is 10 MPa or more, the snow resistance and wind pressure resistance are also excellent.

[0168] The content of the fluororesin relative to the total mass of the substrate is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and may also be 100% by mass. If the content of the fluororesin is above the lower limit value of the above range, the weather resistance of the substrate is more excellent.

[0169] (Other components)

[0170] The substrate may further contain non-fluorine resins, known additives, etc. As known additives, colored pigments, UV absorbers, near-infrared absorbing pigments, and near-infrared reflecting pigments can be cited as examples.

[0171] As colored pigments, titanium oxide as a white pigment, aluminum cobalt oxide as a blue pigment, and iron oxide as a red pigment can be cited as examples.

[0172] As UV absorbers, inorganic UV absorbers, organic UV absorbers, etc. can be cited as examples. As inorganic UV absorbers, inorganic particles such as zinc oxide, titanium oxide, cerium oxide, and iron oxide; inorganic composite particles formed by coating inorganic substances such as silica, alumina, and zirconia on the surface of the above inorganic particles, etc. can be cited as examples.

[0173] As near-infrared absorbing pigments or near-infrared reflecting pigments, boron compounds such as lanthanum hexaboride, tungsten compounds such as cesium tungstate, indium tin oxide, antimony tin oxide, etc. can be cited as examples.

[0174] When the coating film has a light reflection function, from the viewpoint of not hindering the light reflection function of the coating film, the substrate preferably has light transmittance. The total light transmittance of the substrate is preferably 70% or more, more preferably 85% or more. In the present disclosure, the "total light transmittance" is a value measured in accordance with JIS K7375:2008 "Plastics - Method for determining total light transmittance and total light reflectance".

[0175] The thickness of the substrate is preferably 25 to 1000 μm, more preferably 100 to 500 μm. If the thickness of the substrate is above the lower limit value of the above range, the mechanical strength of the substrate is excellent. If the thickness of the substrate is below the upper limit value of the above range, the light transmittance of the substrate is excellent. The shape of the substrate is not particularly limited, and a film is preferred.

[0176] From the viewpoint of excellent adhesion to the coating film, it is preferable to perform a surface treatment for increasing the surface tension on the surface of the substrate where the coating film is formed. By performing the surface treatment, polar groups such as formyl groups, carboxyl groups, and hydroxyl groups are formed on the surface of the substrate, and chemical bonds are formed between the polar groups on the surface of the substrate and the hydroxyl groups of the specific fluororesin contained in the coating film, thereby improving the adhesion between the substrate and the coating film. As the surface treatment, corona discharge treatment, metallic sodium treatment, mechanical roughening treatment, excimer laser treatment, etc. can be cited as examples. From the viewpoints of fast treatment speed and no need for post-treatment cleaning, corona discharge treatment is preferred.

[0177] The surface tension of the substrate is preferably 0.035 N / m or more, more preferably 0.04 N / m or more. If the surface tension of the substrate is at or above the lower limit value of the above range, the adhesion between the substrate and the coating film is more excellent. The upper limit of the surface tension of the substrate is not particularly limited and may be, for example, 0.06 N / m.

[0178] <Coating film>

[0179] The coating film is a film formed on the substrate and formed using the above resin composition. When the resin composition contains a solvent, the coating film refers to the film obtained by applying the resin composition to the substrate and removing the solvent. The coating film may be a cured film obtained by simply applying the resin composition to the substrate and removing the solvent, or may be a cured film obtained by curing the resin composition by heating or the like.

[0180] In the present disclosure, the film formed using the resin composition, whether provided on the entire surface or on a partial surface, is equivalent to the "coating film".

[0181] In one surface of the substrate, the ratio of the area of the coating film to the area of the substrate can be appropriately selected according to the purpose or the like, and is, for example, 10 to 100%. More specifically, the area of the coating film can be, for example, less than 95%, less than 90%, or less than 80% of the total area of one surface of the substrate. In addition, the area of the coating film can be 80% or more, 90% or more, or 95% or more of the total area of one surface of the substrate.

[0182] The coating film can be formed on one surface of the substrate or on both surfaces of the substrate.

[0183] The coating film can be one layer or two or more layers.

[0184] The thickness of the coating film (the total thickness when there are two or more layers) is preferably 0.5 to 10 μm, more preferably 1 to 6 μm. When the thickness of the coating film is below the upper limit value of the above range, the coating film follows the deformation of the substrate such as expansion, contraction, bending, etc., and the coating film tends to be less likely to peel off from the substrate.

[0185] The method for forming the coating film is not particularly limited, and examples thereof include the following methods.

[0186] · A method of applying the resin composition onto the substrate by a known coating method such as gravure printing, screen printing, pad printing, inkjet, brush coating, spray coating, die coating, etc., and removing the solvent when the resin composition contains a solvent, thereby forming a coating film.

[0187] · A method of applying the resin composition onto a transfer film by a known coating method, removing the solvent when the resin composition contains a solvent, thereby forming a coating film, and then transferring the coating film on the transfer film into a substrate shape using a hot roll or the like.

[0188] As a method for forming a coating film, from the viewpoints of alignment accuracy, productivity, etc., gravure printing, screen printing, transfer printing, and inkjet printing are preferred, and gravure printing is more preferred.

[0189] In the coating method, as a method for removing the solvent after coating the resin composition on the substrate, examples include heat drying, reduced-pressure drying, heat reduced-pressure drying, etc. In the case of heat drying or heat reduced-pressure drying, the heating temperature is preferably 30 to 150 °C, more preferably 60 to 120 °C. The drying can be carried out only once or multiple times.

[0190] When the resin composition of the present disclosure is a resin composition containing a curing agent, the resin composition can be cured by heating at, for example, 40 to 80 °C to form a coating film.

[0191] Considering the further formation of a functional layer described later on the coating film surface, surface treatment can be performed on the coating film surface to improve its adhesion. As the surface treatment, examples include the same treatments as those that can be performed on the substrate.

[0192] <Layers other than the substrate and the coating film formed from the resin composition of the present disclosure>

[0193] The laminate may further have layers other than the substrate and the coating formed from the resin composition of the present disclosure.

[0194] For example, the laminate may further have a functional layer on the coating film formed from the resin composition of the present disclosure. The functional layer can be formed by coating, transfer using a transfer film, sputtering, etc. The functional layer can be one layer or two or more layers.

[0195] In the present disclosure, the functional layer refers to a layer that imparts a target function to the laminate. Examples of the target function imparted to the laminate include designability, optical properties (ultraviolet absorption, ultraviolet reflectance, near-infrared absorption, near-infrared reflectance, etc.), durability, etc.

[0196] In the composition for forming the functional layer, as the components for imparting the target function to the laminate, examples include the pigments, UV absorbers, UV reflectors, near-infrared absorption pigments, near-infrared reflectance pigments, curing agents, etc. that are the components of the resin composition as described above.

[0197] The functional layer tends to adhere well to the coating film. One of the reasons is considered that the cellulose acetate resin concentrated on the coating film surface is partially dissolved in the components in the functional layer or is compatible with the components in the functional layer.

[0198] In addition, the laminate may have an adhesive layer between the substrate and the coating film of the resin composition of the present disclosure or between the coating film of the resin composition of the present disclosure and any other layer. As the adhesive layer, examples include a layer formed by coating a silane coupling agent, etc.

[0199] As a preferable layer structure when the laminate has a substrate and a layer other than the above coating film, the following structures can be exemplified.

[0200] · A laminate having a substrate, the above coating film, and a functional layer in this order. If necessary, an adhesive layer is provided between each layer. The functional layer in this case can be for design, curability, adhesion, optical properties, etc.

[0201] · A laminate having a substrate, the above coating film, a first functional layer, and a second functional layer as required in this order. If necessary, an adhesive layer is provided between each layer. The resin composition of the present disclosure can be used in at least one layer selected from the first functional layer and the second functional layer. In this case, the first functional layer can be for curability, adhesion, optical properties, etc., and the second functional layer can be for design, etc.

[0202] 〔Use of the laminate〕

[0203] The use of the laminate of the present disclosure is not particularly limited. As uses of the laminate, examples include membrane structure facilities (sports facilities (swimming pools, gymnasiums, tennis courts, football fields, track and field stadiums, etc.), warehouses, convention halls, exhibition halls, horticultural facilities (horticultural greenhouses, agricultural greenhouses, etc.), arcade roofs, etc. (roof materials, exterior wall materials, skylights, waterproof sheets, curing sheets, etc.); membrane materials for sieves; sound insulation walls; windbreak fences; wave break fences; highway side walls; garage awnings; membrane materials for shopping malls; aisle walls; anti-scattering films for glass; heat-resistant sheets; water-resistant sheets; tent materials for tent warehouses; membrane materials for sunlight control; partial roof materials for daylighting; window materials to replace glass; membrane materials for fire partitions; curtains; membrane materials for exterior wall reinforcement; waterproof membranes; smoke-proof membranes; non-combustible transparent partitions; membrane materials for road reinforcement; interior decoration (lighting, wall surfaces, brands, etc.); exterior decoration (tents, billboards, etc.), automotive materials (car hoods, damping materials, vehicle bodies, etc.); aircraft materials; ship materials; outer casings of household appliances; inner walls of tanks, containers, etc.; filters; membrane materials for construction, etc. In one aspect, the laminate of the present disclosure is particularly suitable for use as a membrane material for membrane structure facilities, sieves, billboards, or sunlight control.

[0204] Examples

[0205] Examples are shown below to explain the embodiments of the present disclosure in detail. However, the embodiments of the present disclosure are not limited to the following examples. Examples 2 to 3, 5 to 7, 9 to 11, and 13 to 24 are examples, and Examples 1, 4, 8, and 12 are comparative examples.

[0206] The materials used in each example are as described below.

[0207] [Specific fluororesin]

[0208] · As the specific fluororesin 1 solution, LF200MEK (manufactured by AGC Inc., solid content: 60% by mass, solvent: methyl ethyl ketone, hydroxyl value: 31 mg(KOH) / g) is used. The main chain of the LF200MEK resin has an alternating copolymer of vinyl fluoride and hydroxyalkyl vinyl ether.

[0209] · As the specific fluororesin 2 solution, LF600 (manufactured by AGC Inc., solid content: 50% by mass, solvent: xylene:ethylbenzene:toluene = 13:12:25 (mass ratio), hydroxyl value: 27 mg(KOH) / g) is used. The main chain of the LF600 resin has an alternating copolymer of vinyl fluoride and hydroxyalkyl vinyl ether.

[0210] [Specific aluminum composite particles]

[0211] As the specific aluminum composite particles, a paste-like aluminum paste EMR-D5660 (trade name, manufactured by Toyo Aluminum Co., Ltd.) containing a liquid medium is used. This aluminum paste contains 49.5% by mass of flat particles and 50.5% by mass of propylene glycol monomethyl ether as a solvent. Among the above flat particles, the surface of the flat aluminum is coated with 15% by mass of silica based on 100% by mass of aluminum. The average value of the major axis of this aluminum composite is 9 μm.

[0212] [Esterified cellulose resin]

[0213] The following resins are used as the esterified cellulose resin.

[0214] · Esterified cellulose resin 1: CAB-381-2 (trade name, manufactured by Eastman Chemical Japan Co., Ltd.; glass transition temperature 133 °C, number average molecular weight 40,000, hydroxyl content 1.3% by mass)

[0215] · Esterified cellulose resin 2: CAB-551-0.01 (trade name, manufactured by Eastman Chemical Japan Co., Ltd.; glass transition temperature 85 °C, number average molecular weight 16,000, hydroxyl content 1.5% by mass)

[0216] · Esterified cellulose resin 3: CAP-482-0.5 (trade name, manufactured by Eastman Chemical Japan Co., Ltd.; glass transition temperature 142 °C, number average molecular weight 25,000, hydroxyl content 2.6% by mass)

[0217] Each esterified cellulose resin is dissolved in methyl ethyl ketone (MEK) to prepare a CAB solution or a CAP solution with a solid content concentration of 20%, and then blended as a component of the coating.

[0218] [Curing agent]

[0219] Polyisocyanate using hexamethylene diisocyanate (trade name: DURANATE A201H, manufactured by Asahi Kasei Corporation). The NCO content of this curing agent is 17.2% by mass.

[0220] [UV Absorbent]

[0221] Tinuvin 479 of the hydroxyphenyltriazine type (manufactured by BASF Japan Ltd.) is used as the UV absorbent.

[0222] The evaluation methods in the examples and comparative examples are as described below.

[0223] <Evaluation Method>

[0224] (Adhesion)

[0225] According to JIS K5600-5-6:1999, 10×10 square grid incisions of 1 mm each are made on the coating film formed on the fluororesin film, and a transparent tape Cellotape (manufactured by Nichiban Co., Ltd.: trade name CT18) is pasted. After peeling off the tape, the number of peeled squares among 100 squares is checked, and the adhesion is evaluated according to the following evaluation criteria. This test method is also called the cross-cut Cellotape (registered trademark) peel test.

[0226] A: Excellent (more than 0 squares and less than 2 squares are peeled off)

[0227] B: Good (more than 2 squares and less than 20 squares are peeled off)

[0228] C: Poor (more than 20 squares are peeled off)

[0229] An evaluation of A or B is considered qualified.

[0230] (Visible Light Transmittance, Visible Light Reflectance)

[0231] The visible light transmittance and visible light reflectance of the coating film are measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100PC) in accordance with JIS R3106:1998 ("Test Methods for Transmittance, Reflectance, Emissivity, and Solar Heat Gain Coefficient of Glass Sheets"). These optical properties are measured by irradiating light from the fluororesin film side. The visible light reflectance was measured for the coating film with specific aluminum composite particles as the main pigment for brightness, and the visible light transmittance was measured for the coating film with titanium oxide, aluminum cobalt oxide, or copper phthalocyanine green as the main pigment.

[0232] (Adhesion Test)

[0233] Overlap the coated film surfaces printed on the fluororesin film, place a metal plate to apply a pressure of 10 N / cm 2 , and put it into a thermostatic bath maintained at a certain temperature for 15 hours. Then, it is restored to 25 °C. After 1 hour, peel off the overlapping fluororesin films. At this time, those with partial adhesion between the coatings are judged to have adhesion. The test temperature range is 30 to 70 °C, with an increment of 5 °C.

[0234] The qualified temperature for the adhesion test refers to the highest temperature at which no adhesion occurs. For example, when the qualified temperature for the adhesion test is 40 °C, it means no adhesion at 40 °C but adhesion at 45 °C. When the qualified temperature for the adhesion test is 45 °C or higher, it is comprehensively judged as qualified.

[0235] (Accelerated weathering test)

[0236] An accelerated weathering test of 5000 hours was carried out using a sunshine weathering test machine equipped with a carbon arc lamp in accordance with JIS K7350-4:2008 (manufactured by Suga Test Instruments Co., Ltd., product name: 300 Sunshine WeatherMeter). The accelerated weathering test was carried out for both the top exposure where light is incident from the coating side and water is sprayed onto the coating side, and the back exposure where light is incident from the substrate side and water is sprayed onto the substrate side. After the accelerated weathering test, the adhesion of the coating film was evaluated.

[0237] [Example 1]

[0238] The surface of a 250-μm ETFE film (manufactured by AGC Inc., product name: Fluon ETFE Film 250NJ) was subjected to corona discharge treatment in air at a treatment density of 150 W·min / m 2 . The surface tension of the surface subjected to corona discharge treatment was 0.054 N / m.

[0239] A coating was prepared according to the formulation shown in Table 1. A specific fluororesin 1 solution, a specific aluminum complex particle paste, and a mixed solvent of toluene / MEK = 50 / 50 (mass ratio) were mixed and stirred to obtain a silver paste. The viscosity of the coating on a No. 3 Zahn cup was 25 seconds.

[0240] Next, the prepared coating was gravure-printed on the corona discharge-treated surface of the ETFE film and dried at 120 °C for 1 minute to obtain a laminate. The thickness of the coating film was 2 μm. The formulation of the coating, the content rate in the coating after removing the solvent, and the evaluation results are shown in Table 1.

[0241] [Examples 2 to 18]

[0242] A laminate was obtained in the same manner as in Example 1, except that the coating formulation was changed. A mixed solvent of toluene / MEK = 50 / 50 (mass ratio) was mixed so that the viscosity of the coating on a No. 3 Zahn cup was 22 - 26 seconds. The thickness of the dried coating film was 2 μm in each case. The coating formulation, the content in the solvent-removed coating, and the evaluation results are shown in Tables 1 and 2.

[0243] In Examples 1 to 18, it was confirmed that the adhesiveness and the sealing property of Examples 2, 3, 5 to 7, 9 to 11, 13 to 18 using the resin composition of the present disclosure were excellent.

[0244] On the other hand, in Example 1, Example 12 where CAB was not added, and Example 4 where the content of CAB was less than 0.2 parts by mass relative to 100 parts by mass of a specific fluororesin 1, the pass temperature of the adhesion test was lower than 45°C.

[0245] In Example 8 where the content of CAB exceeded 9 parts by mass relative to 100 parts by mass of a specific fluororesin 1, the sealing property was insufficient.

[0246] In Examples 9 to 11, 14, 16, and 18 using a curing agent, it was confirmed that the pass temperature of the adhesion test was high.

[0247] [Examples 19 - 20]

[0248] Coatings were prepared according to the formulations shown in Table 3. In Examples 19 and 20, the viscosity of the coatings on a No. 3 Zahn cup was also 25 seconds. Subsequently, a laminate was obtained in the same manner as in Example 1.

[0249] In Examples 19 and 20, the coating film formed from the prepared coating was used as a transparent undercoat, and a UV-curable acrylic ink was inkjet-printed on the coating film using LEC-540 (manufactured by Roland DG Co., Ltd.), and UV curing was performed using the UV irradiation mechanism built into the printing apparatus to obtain a laminate. The coating formulation, the content in the solvent-removed coating, and the evaluation results are shown in Table 1. From this, it can be seen that this coating film is also useful as an undercoat for inkjet printing or as an undercoat for further forming a coating film using a solvent-containing coating.

[0250] In addition, the coating prepared in Example 2 was gravure-printed on the coating films prepared in Examples 19 and 20, and a cross-cut transparent tape Cellotape (registered trademark) peel test was performed on the formed coating films. As shown in Table 3, the sealing property of the coating film made from the coating prepared in Example 2 was excellent.

[0251] In the coating films prepared in Examples 2 to 3, 5 to 7, 9 to 11, and 13 to 20, in the cross-cut Cellotape (registered trademark) peel test, the coating film did not turn into a cohesive failure mode that adhered to both the transparent tape and the fluororesin film, and maintained good cohesion.

[0252] [Table 1]

[0253]

[0254] [Table 2]

[0255]

[0256] [Table 3]

[0257]

[0258] [Examples 21 to 24]

[0259] Except for changing the coating formulation, laminates were obtained in the same manner as in Example 1. A mixed solvent of toluene / MEK = 50 / 50 (mass ratio) was mixed so that the viscosity of the coating on a No. 3 Zahn cup was 22 to 26 seconds. The thickness of the dried coating film was 2 μm. The coating formulation, the content rate in the solvent-removed coating, and the evaluation results are shown in Tables 4 and 5.

[0260] In Examples 21 to 24, the qualified temperature for the adhesion test was 45°C, and the comprehensive judgment was qualified. In addition, in the cross-cut Cellotape (registered trademark) peel test after the initial and weather resistance tests, the evaluation results were all A, indicating sufficient adhesion and cohesion to the film.

[0261] [Table 4]

[0262]

[0263] [Table 5]

[0264]

[0265] The entire disclosure of Japanese Patent Application No. 2020-170122 is incorporated herein by reference.

[0266] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and separately indicated to be incorporated by reference.

[0267] Symbol Explanation

[0268] 10 laminate

[0269] 12 substrate

[0270] 14 Coating film

[0271] L Sunlight.

Claims

1. A resin composition comprising a copolymer having a fluoroolefin unit and a hydroxy group-containing monomer unit, and an esterified cellulose resin, wherein the content of the esterified cellulose resin is 0.2 to 5.00 parts by mass relative to 100 parts by mass of the copolymer having a fluoroolefin unit and a hydroxy group-containing monomer unit. The fluoroolefin includes at least one selected from vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, and (perfluoroalkyl)ethylene. The proportion of the fluoroolefin unit in all the units of the copolymer is 30 to 70 mol%. The hydroxy group-containing monomer includes at least one selected from allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, (meth)acrylic acid hydroxyalkyl ester, vinyl ester of hydroxyalkyl carboxylic acid, and allyl ester of hydroxyalkyl carboxylic acid. The proportion of the hydroxy group-containing monomer unit in all the units of the copolymer is 0.5 to 20 mol%. The hydroxy group content of the esterified cellulose resin is 0.1 to 10% by mass, and the glass transition temperature of the esterified cellulose resin is 80°C or higher and 200°C or lower.

2. The resin composition according to claim 1. Characterized in that The esterified cellulose resin includes at least one selected from cellulose acetate butyrate resin and cellulose acetate propionate resin.

3. The resin composition according to claim 1. Characterized in that It does not contain a curing agent; or It contains a curing agent, and the molar ratio of the curable group in the curing agent to the hydroxy group in the copolymer having a fluoroolefin unit and a hydroxy group-containing monomer unit is 0.5 or less.

4. The resin composition according to any one of claims 1 to 3, which is a coating applied to a substrate containing a fluororesin.

5. A laminate comprising a substrate and a coating film formed from the resin composition according to any one of claims 1 to 3.

6. The laminate according to claim 5. Characterized in that The substrate contains a fluororesin.

7. The laminate according to claim 6. Characterized in that The fluororesin includes at least one selected from vinyl fluoride polymer, vinylidene fluoride polymer, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-vinylidene fluoride-propylene copolymer, ethylene-tetrafluoroethylene copolymer, hexafluoropropylene-tetrafluoroethylene copolymer, ethylene-hexafluoropropylene-tetrafluoroethylene copolymer, perfluoro(alkyl vinyl ether)-tetrafluoroethylene copolymer, chlorotrifluoroethylene polymer, and ethylene-chlorotrifluoroethylene copolymer.

8. The laminate according to claim 5. Characterized in that It is a film material for membrane structure facilities, sieves, billboards, or solar light regulation.

Images