Resin Composition and Laminate

Abstract

This resin composition contains an esterified cellulose resin and a copolymer that includes a fluoroolefin unit and a monomer unit having a hydroxyl group. The esterified cellulose resin content is 0.2 to 9 parts by mass per 100 parts by mass of the copolymer that includes a fluoroolefin unit and a monomer unit having a hydroxyl group. This layered body is provided with a coating that is 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 are used as film materials (roof materials, exterior wall materials, etc.) in membrane structure facilities (sports facilities (pools, gymnasiums, tennis courts, soccer fields, track and field stadiums, etc.), warehouses, assembly halls, exhibition halls, horticultural facilities (greenhouses, agricultural houses, etc.), etc.) because of their excellent weather resistance, stain resistance, etc. However, since fluororesin films have a high solar transmittance, when used as a film material for a membrane structure facility that receives sunlight, the inside of the membrane structure facility may be too bright or the temperature inside the membrane structure facility may rise too much. Therefore, the solar reflectance may be increased by printing a paint on the fluororesin film. In addition, team colors, logos, etc. of the team using the sports facility may be printed on the film with a paint.

[0003] As the paint applied to the fluororesin film, a paint 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 containing a fluororesin having a mass average molecular weight in a specific range and having specific functional groups in a specific ratio, and a solvent, for application on a fluororesin substrate.

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The coating film formed by the paint is often arranged with the printed surfaces facing each other for protection from abrasion due to contact with rain, pebbles, sand, etc., and friction with aggregates that hold the film. Also, two-layer films with facing printed surfaces may be fabricated, transported to the site, spread out, and inflated with air. There is a problem that blocking occurs when the coating films come into contact with each other.

[0007] On the other hand, since the film for membrane structure is used by itself as a membrane material for roofs, walls, etc., it is constantly repeating deformation and recovery, such as deformation of the film due to snow load, vibration due to wind, and stamping by raindrops. The paint printed on such a film is required to have high adhesion so that it does not peel off even when the film is deformed.

[0008] However, in the methods described in Patent Documents 1 and 2, there is room for improvement in achieving both adhesion and blocking resistance.

[0009] The present disclosure relates to providing a resin composition having excellent adhesion and blocking resistance, and a laminate including a coating film formed from the resin composition.

Means for Solving the Problems

[0010] The means for solving the above problems include the following aspects. <1> A copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group, and an esterified cellulose resin, A resin composition, 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 monomer unit having a hydroxyl group. <2> The resin composition according to <1>, wherein the hydroxyl group content of the esterified cellulose resin is 0.1 to 10% by mass. <3> The resin composition according to <1> or <2>, wherein the esterified cellulose resin contains at least one selected from the group consisting of cellulose acetate butyrate resin and cellulose acetate propionate resin. <4> The resin composition according to any one of <1> to <3>, wherein the fluoroolefin contains at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, and (perfluoroalkyl)ethylene. <5> The resin composition according to any one of <1> to <4>, wherein the monomer having a hydroxyl group contains at least one selected from the group consisting of allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl (meth)acrylate, hydroxyalkyl vinyl carboxylate, and hydroxyalkyl allyl carboxylate. <6> Does not contain a curing agent, or Contains a curing agent, and the molar ratio of the curable group in the curing agent to the hydroxyl group in the copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group is 0.5 or less. The resin composition according to any one of <1> to <5>. <7> The resin composition according to any one of <1> to <6>, which is a paint for applying to a substrate containing a fluororesin. <8> A laminate comprising a substrate and a coating film formed of the resin composition according to any one of <1> to <6>. <9> The laminate according to <8>, wherein the substrate contains a fluororesin. <10> The laminate according to <9>, wherein the 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. <11> The laminate according to any one of <8> to <10>, which is a film material for a membrane structure facility, a screen, a signboard, or solar radiation control.

Advantages of the Invention

[0011] According to the present disclosure, there is provided a resin composition having excellent adhesion and blocking resistance, and a laminate including a coating film formed of the resin composition.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present disclosure will be described in detail, but the embodiments of the present disclosure are not limited to the following embodiments. In the present disclosure, the term "step" includes, in addition to a step independent of other steps, a step that cannot be clearly distinguished from other steps but whose purpose is achieved. In the present disclosure, in the numerical range indicated by using "~", the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively. 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, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. When describing an embodiment with reference to the drawings in the present disclosure, the configuration of the embodiment is not limited to the configuration shown in the drawings. Also, the sizes of the members in each figure are conceptual, and the relative relationship of the sizes between the members is not limited thereto. Further, in each drawing, members having substantially the same function may be given the same reference numeral throughout the drawings, and duplicate descriptions may be omitted. In the present disclosure, "unit" means a part derived from a monomer that exists in a polymer and constitutes the polymer. Also, a structure obtained by chemically converting the structure of a certain unit after polymer formation is also referred to as a unit. In some cases, a unit derived from an individual monomer is called by a name obtained by adding "unit" to the monomer name. In the present disclosure, films and sheets are referred to as "films" regardless of their thickness. In the present disclosure, acrylate and methacrylate are collectively referred to as "(meth)acrylate".

[0014] ≪Resin Composition≫ The resin composition of the present disclosure contains a copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group (hereinafter, also referred to as "specific fluororesin"), and 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 copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group. In the resin composition of the present disclosure, excellent adhesion to the substrate and antiblocking properties are achieved simultaneously.

[0015] Generally, an esterified cellulose resin adheres to a PET film, a polystyrene film, etc. that have been surface-treated by corona discharge, plasma discharge, etc., but it is difficult to adhere to a fluororesin film even when surface-treated by the same method. Also, the fluororesin and the esterified cellulose resin are not compatible in any ratio and are not easily entangled with each other. Therefore, in a fluororesin-containing resin composition for imparting to a fluororesin film, it is generally considered difficult to apply an esterified cellulose resin. However, simply blending a small amount of an esterified cellulose resin with a specific fluororesin can significantly improve the blocking resistance and also maintain the adhesion to the fluororesin film. In particular, when 0.2 parts by mass of an esterified cellulose resin is blended with 100 parts by mass of a specific fluororesin, an improvement in the blocking temperature can be observed. This is presumably due to the uneven distribution of the esterified cellulose resin with a high glass transition point on the surface layer of the resin composition in contact with the outside air during the drying of the applied resin composition. Hereinafter, each component of the resin composition will be described in detail.

[0016] <Specific fluororesin> The resin composition contains a copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group (i.e., a specific fluororesin). Since the specific fluororesin has a monomer unit having a hydroxyl group in addition to the fluoroolefin unit, it has good adhesion to the substrate in addition to the properties of a fluororesin such as weather resistance and stain resistance. The specific fluororesin may or may not have other monomer units in addition to the fluoroolefin unit and the monomer unit having a hydroxyl group. The specific fluororesin may be used alone or in combination of two or more.

[0017] As the fluoroolefin, a fluoroolefin having 10 or less carbon atoms is preferable. Specifically, 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. may be mentioned. (Perfluoroalkyl)ethylene is a fluoroolefin represented by CH2=CH-Rf (wherein Rf represents a perfluoroalkyl group). Specifically, (perfluoromethyl)ethylene, (perfluorobutyl)ethylene, etc. may be mentioned. As the (perfluoroalkyl)ethylene, a (perfluoroalkyl)ethylene having 3 to 8 carbon atoms is preferable. The perfluoroalkyl may be linear or branched. As the fluoroolefin other than (perfluoroalkyl)ethylene, a fluoroolefin having 2 or 3 carbon atoms is preferable.

[0018] The monomer having a hydroxyl group in the monomer unit having a hydroxyl group may be a monomer having a fluorine atom or a monomer not having a fluorine atom, and it is preferable that it is a monomer not having a fluorine atom. Examples of the monomer having a hydroxyl group include allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl (meth)acrylate, hydroxyalkyl vinyl carboxylate, hydroxyalkyl allyl carboxylate, etc. In the monomer having a hydroxyalkyl group, the alkyl group of the hydroxyalkyl group may be linear, branched or cyclic, or a combination thereof. Further, when the alkyl group is a combination of two or more of these, the hydroxy group may be located at any position. The hydroxyalkyl group of the monomer having a hydroxyalkyl group may be a hydroxycycloalkyl group, a hydroxyalkyl-substituted cycloalkyl group, etc. The carbon number of the hydroxyalkyl group is preferably 10 or less, more preferably 6 or less. Examples of the hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and the like. Examples of the hydroxyalkyl allyl ether include 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 4-hydroxycyclohexyl allyl ether, and the like. Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate and the like. Examples of the vinyl hydroxyalkyl carboxylate include vinyl hydroxyacetate, vinyl hydroxyisobutyrate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxycyclohexanecarboxylate, and the like. Examples of the allyl hydroxyalkyl carboxylate include allyl hydroxyacetate, allyl hydroxypropionate, allyl hydroxybutyrate, allyl hydroxyisobutyrate, allyl hydroxycyclohexanecarboxylate, and the like.

[0019] Examples of the monomer unit other than the fluoroolfin unit and the monomer unit having a hydroxyl group include a unit derived from a fluorine-containing monomer other than a fluoroolfin, a unit derived from a monomer having no fluorine atom, and the like. Examples of the fluorine-containing monomer other than a fluoroolfin include perfluoro(alkyl vinyl ether), perfluoro unsaturated cyclic ether, and the like. As the perfluoro(alkyl vinyl ether), perfluoro(alkyl vinyl ether) having 10 or less carbon atoms is preferable, and 6 or less carbon atoms is more preferable. Specifically, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), perfluoro(heptyl vinyl ether), and the like can be mentioned. Examples of the monomer having no fluorine atom include olefins, vinyl ethers, allyl ethers, vinyl carboxylates, allyl carboxylates, unsaturated carboxylic acid esters, etc. Except for olefins, the carbon number of the monomer is preferably 16 or less, more preferably 12 or less. As the olefin, olefins having 2 to 4 carbon atoms are preferable, and examples thereof include ethylene, propylene, isobutylene, etc. Examples of the vinyl ether 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.). Examples of the allyl ether include alkyl allyl ethers (such as ethyl allyl ether, hexyl allyl ether, etc.). Examples of the vinyl carboxylate include vinyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid, etc.). Further, as the vinyl ester of a carboxylic acid having a branched alkyl group, Veova 9 (registered trademark), Veova 10 (registered trademark), etc. manufactured by Shell Chemical Co., Ltd. may be used. Examples of the allyl carboxylate include allyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid, etc.). Examples of the unsaturated carboxylic acid ester 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-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.

[0020] In addition, the specific fluororesin may further have a monomer unit having a crosslinkable group other than a hydroxyl group, for example, a carboxy group, an amide group, an epoxy group, etc.

[0021] As a combination of a fluoroolefin unit and a monomer unit having a hydroxyl group in a specific fluororesin, a combination of at least one selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene and a hydroxyalkyl vinyl ether is particularly preferable.

[0022] In the specific fluororesin, the proportion of the fluoroolefin unit is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, based on all the units of the specific fluororesin. When the proportion of the fluoroolefin unit is at least the lower limit of the above range, a coating film excellent in weather resistance, stain resistance, etc. tends to be obtained. When the proportion of the fluoroolefin unit is at most the upper limit of the above range, the adhesion between the substrate and the coating film tends to be further excellent.

[0023] In the specific fluororesin, the proportion of the monomer unit having a hydroxyl group is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%, based on all the units of the specific fluororesin. When the proportion of the monomer unit having a hydroxyl group is at least the lower limit of the above range, the adhesion between the coating film and the substrate tends to be further excellent. When the proportion of the monomer unit having a hydroxyl group is at most the upper limit of the above range, the flexibility of the coating film tends to be excellent.

[0024] The proportion of the monomer unit in the fluororesin can be confirmed by a nuclear magnetic resonance apparatus (NMR).

[0025] In one aspect, as the specific fluororesin, a copolymer having a fluoroolefin unit, a monomer unit having a hydroxyl group, and a non-fluorine-based monomer unit having no hydroxyl group is preferable. Hereinafter, such a copolymer is also referred to as "copolymer (A)".

[0026] As a combination of the monomers constituting the copolymer (A), from the viewpoints that the solar reflectance of the coating film hardly decreases over a long period when the resin composition is used for forming a solar reflective layer, the adhesion between the coating film and the substrate is excellent, and the flexibility of the coating film is excellent, the following combination (1) is preferable, and combination (2) or (3) is more preferable.

[0027] Combination (1) · Fluoroolefin: tetrafluoroethylene or chlorotrifluoroethylene · Monomer having a hydroxyl group: hydroxyalkyl vinyl ether · Non-fluorine-based monomer having no hydroxyl group: at least one selected from the group consisting of cycloalkyl vinyl ether, alkyl vinyl ether, and vinyl carboxylate

[0028] Combination (2) · Fluoroolefin: tetrafluoroethylene · Monomer having a hydroxyl group: hydroxyalkyl vinyl ether · Non-fluorine-based monomer having no hydroxyl group: at least one selected from the group consisting of tert-butyl vinyl ether and vinyl carboxylate

[0029] Combination (3) · Fluoroolefin: chlorotrifluoroethylene · Monomer having a hydroxyl group: hydroxyalkyl vinyl ether · Non-fluorine-based monomer having no hydroxyl group: at least one selected from the group consisting of tert-butyl vinyl ether and vinyl carboxylate

[0030] The proportion of fluoroolefin units in the copolymer (A) is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, out of all the units (100 mol%) of the copolymer (A). When the proportion of fluoroolefin units is at least the lower limit of the above range, a coating film excellent in weather resistance, stain resistance, etc. tends to be obtained. When the proportion of fluoroolefin units is at most the upper limit of the above range, the adhesion between the substrate and the coating film tends to be further excellent.

[0031] The proportion of monomer units having a hydroxyl group in the copolymer (A) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol% based on all the units of the copolymer (A). When the proportion of monomer units having a hydroxyl group is at least the lower limit of the above range, the adhesion between the coating film and the substrate tends to be further improved. When the proportion of monomer units having a hydroxyl group is at most the upper limit of the above range, the flexibility of the coating film tends to be excellent.

[0032] The proportion of non-fluorine monomer units having no hydroxyl group in the copolymer (A) is preferably 20 to 60 mol%, more preferably 30 to 50 mol% based on all the units of the copolymer (A). When the proportion of the monomer units is at least the lower limit of the above range, the flexibility of the coating film tends to be excellent. When the proportion of the monomer units is at most the upper limit of the above range, the adhesion between the coating film and the substrate tends to be further improved.

[0033] Commercially available products of the copolymer (A) include Lumiflon (registered trademark) series (LF200, LF100, LF710, LF600, etc.) (AGC Inc.), Zefluor (registered trademark) GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) (Daikin Industries, Ltd.), Fluonate (registered trademark) series (K-700, K-702, K-703, K-704, K-705, K-707, etc.) (manufactured by DIC Corporation), ETERFLON series (4101, 41011, 4102, 41021, 4261A, 4262A, 42631, 4102A, 41041, 41111, 4261A, etc.) (manufactured by Eternal Chemical), and the like.

[0034] 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 a value measured by Method A of ISO 14900:2001.

[0035] The content rate of the specific fluororesin in the resin composition may be 30% by mass or more, 40% by mass or more, or 50% by mass or more with respect to the total mass of the resin composition. Also, the content rate of the specific fluororesin in the resin composition may be 90% by mass or less, or 80% by mass or less with respect to the total mass of the resin composition. From such a viewpoint, the content rate of the specific fluororesin in the resin composition may be 30 to 90% by mass, 40 to 80% by mass, or 50 to 80% by mass with respect to the total mass of the resin composition.

[0036] <Esterified cellulose resin> 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 the content of the esterified cellulose resin with respect to the specific fluororesin being within the above range, good adhesion and antiblocking properties can be achieved simultaneously. Also, as described above, generally, the esterified cellulose resin does not have high compatibility with the fluororesin, and thus the cohesive force tends to decrease when mixed with the fluororesin. However, in the resin composition of the present disclosure, when the content of the esterified cellulose resin is within the above range, a decrease in the cohesive force of the coating film can be suppressed.

[0037] 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, preferably 0.5 to 7 parts by mass, and more preferably 1 to 5 parts by mass. When the content of the esterified cellulose resin is at least the lower limit value of the above range, good antiblocking properties can be obtained, and when it is at most the upper limit value of the above range, in particular, the adhesion to the fluororesin substrate of the resin composition after the weather resistance test is excellent. 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 even more preferably 1.00 to 5.00 parts by mass with respect to 100 parts by mass of the specific fluororesin. The masses of the specific fluororesin and the esterified cellulose resin in the resin composition are quantified by taking advantage of the difference in solubility. For example, by dissolving the specific fluororesin in a solvent (such as toluene) in which the esterified cellulose resin does not dissolve and the specific fluororesin dissolves, the mass of each component can be determined and the mass ratio can be calculated. Also, the presence and amount of the esterified cellulose resin present in the resin composition can be confirmed by measuring the infrared absorption spectrum.

[0038] Also, from the viewpoint of antiblocking properties, the content of the esterified cellulose resin is preferably 1 part by mass or more, may be 2 parts by mass or more, and may be 3 parts by mass or more with respect to 100 parts by mass of the specific fluororesin. Until the content of the esterified cellulose resin with respect to 100 parts by mass of the specific fluororesin reaches about 5 parts by mass, a tendency has been found that the blocking temperature increases as the amount increases. On the other hand, even if the amount of the esterified cellulose resin is increased beyond 5 parts by mass, although the blocking temperature is maintained, it does not further increase. Therefore, from the viewpoint of excellent adhesion to the substrate, cohesive force of the coating film, etc., the content of the esterified cellulose resin with respect to 100 parts by mass of the specific fluororesin may be 8 parts by mass or less, may be 7 parts by mass or less, may be 6 parts by mass or less, and may be 5 parts by mass or less. 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, and may be 3.00 parts by mass or more with respect to 100 parts by mass of the specific fluororesin. Also, the content of the esterified cellulose resin with respect to 100 parts by mass of the specific fluororesin 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, and may be 5.00 parts by mass or less.

[0039] Examples of the esterified cellulose resin include cellulose acetate resin, cellulose acetate butyrate (CAB) resin, cellulose acetate propionate (CAP) resin, etc. Generally, CAP is obtained by triesterifying cellulose with acetic acid and propionic acid and then hydrolyzing it. Also, CAB is obtained by triesterifying cellulose with acetic acid and butyric acid and then hydrolyzing it. The esterified cellulose resin is preferably at least one selected from the group consisting of CAB and CAP. The esterified cellulose resin may be used alone or in combination of two or more.

[0040] The properties of the esterified cellulose resin can be indicated by the molecular weight, glass transition point, hydroxyl group content, acetyl group content, butyryl group content, propionyl group content, etc.

[0041] The hydroxyl group content of the esterified cellulose resin is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass. When the hydroxyl group content is within the above range, it is considered to be relatively compatible with the fluororesin and easily maintain the cohesive force when formed into a coating film. When the hydroxyl group content of the esterified cellulose resin is below the upper limit value of the above range, the water absorption rate of the coating film formed by the resin composition is suppressed, and good weather resistance can be obtained. In particular, it is useful in that good weather resistance can be obtained even when the resin composition does not contain a curing agent or the content of the curing agent is suppressed. Also, when the amount of water in the coating film is suppressed, the photodegradation of the fluororesin is suppressed, and thereby the decrease in the adhesion of the coating film can also be suppressed. In particular, when pigments such as aluminum-based pigments and titanium oxide are generally used, the adhesion is likely to decrease due to photodegradation. It is useful in that the decrease in adhesion can be suppressed even when these pigments are used.

[0042] When the esterified cellulose resin is CAB, the acetyl group content in the CAB is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. Also, the butyryl group content in the CAB is preferably 10 to 60% by mass, more preferably 20 to 55% by mass. When the butyryl group content is high, the solubility in organic solvents is excellent.

[0043] When the esterified cellulose resin is CAP, the acetyl group content in the CAP is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. Also, the Propionyl group content is preferably 30 to 60% by mass, more preferably 40 to 50% by mass. Propionyl When the group content is high, the solubility in organic solvents is excellent.

[0044] The hydroxyl group content, acetyl group content, butyryl group content, and propionyl group content of the esterified cellulose resin are values determined by ASTM D817 - 12(2019):Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate.

[0045] The number average molecular weight of the esterified cellulose resin is preferably 12,000 to 75,000, more preferably 20,000 to 50,000. When the number average molecular weight is at least the lower limit value of the above range, the addition effect of cellulose is more favorably exerted, and when it is at most the upper limit value of the above range, a resin composition having a viscosity excellent in gravure printability can be obtained. The number average molecular weight of the esterified cellulose resin is measured by gel permeation chromatography (GPC). Specifically, it is measured in terms of polystyrene using tetrahydrofuran with a gel permeation chromatography apparatus (GPC apparatus: manufactured by Tosoh Corporation, HLC - 8320GPC, column: TSKgelα - M).

[0046] From the viewpoint of further improving the blocking resistance, 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 glass transition temperature is not particularly limited. For example, the glass transition temperature may be 200°C or lower. The glass transition temperature of the esterified cellulose resin is a value measured by the dynamic viscoelasticity measurement (DMA) method.

[0047] Commercially available products of the esterified cellulose resin 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 preferable.

[0048] <Hardener> The resin composition of the present disclosure may or may not contain a hardener. When the resin composition contains a hardener, there is a tendency for improvement in water resistance, solvent resistance, and blocking resistance. In particular, when a hardener is blended, the blocking temperature tends to further increase. On the other hand, from the viewpoint of adhesion to the fluororesin substrate, it is preferable that the resin composition does not contain a hardener or contains only a small amount. Also, for example, in the case of film structure applications, etc., when joining substrates by thermal pressure bonding or the like, it may be necessary to remove the coating film applied to the substrate. Although it is possible to physically remove the coating film using sandblasting, a grinder, etc., when wiping the coating film using a solvent, the coating film that has undergone a chemical curing reaction due to the use of a hardener may not be easily wiped off. Therefore, from the viewpoint of facilitating wiping, it is preferable to suppress the content of the hardener. According to the resin composition of the present disclosure, excellent blocking resistance can be obtained even with a small content of the hardener.

[0049] The curing agent can be appropriately selected from curing agents known as curing agents for paints. Specifically, isocyanate-based curing agents, blocked isocyanate-based curing agents, aminoplast-based curing agents, polyvalent carboxylic acid-based curing agents, polyvalent amine-based curing agents, etc. can be mentioned. The selection of the curing agent is preferably carried out in consideration of the type of curing reactive sites possessed by the fluororesin, curing characteristics, etc. As the curing agent to be used in combination with a specific fluororesin, an isocyanate-based curing agent, a blocked isocyanate-based curing agent, or an aminoplast-based curing agent is preferred. The curing agent may be used alone or in combination of two or more.

[0050] From the above viewpoints, the resin composition either does not contain a curing agent, or even 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 (that is, the number of moles of curable groups in the curing agent / the number of moles of hydroxyl groups in the specific fluororesin) is preferably 1.0 or less, more preferably 0.5 or less, and even more preferably 0.4 or less. The molar ratio may be 0.3 or less, or may be 0.2 or less. From the viewpoint of excellent water resistance, solvent resistance, and blocking resistance, when a curing agent is blended, the 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 group in the specific fluororesin. For example, when assuming an isocyanate group-containing curing agent as the curing agent, the resin composition either does not contain the isocyanate group-containing curing agent, or the molar ratio of the isocyanate groups in the isocyanate group-containing curing agent to the hydroxyl groups in the specific fluororesin in the resin composition ([NCO] / [OH]) is preferably within the above range.

[0051] When using a curing agent that causes a curing reaction at 25°C, it is preferable to prepare separately a main agent containing the specific fluororesin and the curing agent, and to make it a two-component curing type resin composition that is mixed at the time of forming a coating film. Other components that do not react with the specific fluororesin are preferably contained in the main agent. When using a two-component curing type resin composition, the resin composition obtained by mixing the main agent and the curing agent is applied onto a substrate and dried at room temperature, whereby a coating film is formed on the substrate. Also, when using a curing agent that causes a curing reaction by heating, the curing agent and a specific fluororesin can coexist in the resin composition, resulting in a one-component curable resin composition. In this case, the resin composition is applied onto a substrate and baked to form a coating film on the substrate.

[0052] Examples of curing agents that cause a curing reaction at 25°C include non-yellowing diisocyanates (such as hexamethylene diisocyanate and isophorone diisocyanate), polyvalent isocyanate-based curing agents (such as adducts or polymers of the non-yellowing diisocyanates), and the like. Examples of curing agents that cause a curing reaction by heating include blocked isocyanate-based curing agents, aminoplast-based curing agents, and the like. In particular, polyisocyanate-based curing agents containing isocyanate groups are useful. In this case, it is preferable to further add a curing catalyst such as dibutyltin dilaurate to promote curing.

[0053] <Other Components> The resin composition of the present disclosure may 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 also contain various additives such as pigments, UV absorbers, near-infrared absorbing pigments, near-infrared reflecting pigments, blocking improvers, and lubricants. These components may be used alone or in combination of two or more.

[0054] (Resins other than the specific fluororesin and the esterified cellulose resin) Examples of resins other than the specific fluororesin and the esterified cellulose resin include polyester resins, acrylic resins, epoxy resins, and fluororesins other than the specific fluororesin. Examples of fluororesins other than the specific fluororesin include tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (hereinafter also referred to as "THV"), fluoroethylene-vinyl ester copolymer, polytetrafluoroethylene (hereinafter also referred to as "PTFE"), and the like.

[0055] When the resin composition contains a resin other than the specific fluororesin and the esterified cellulose resin, the content of the resin is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the resins in the resin composition. When referring to the content or proportion of the resin, if the component used as an additive is a resin, the content or proportion shall be the content or proportion including the resin used as an additive.

[0056] (Pigment) 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 which is a black pigment, iron oxide which is a red pigment, aluminum cobalt oxide which is a blue pigment, copper phthalocyanine which is a blue pigment or a green pigment, perylene which is a red pigment, and bismuth vanadate which is a yellow pigment.

[0057] The resin composition of the present disclosure may contain an aluminum-based pigment in order to adjust the visible light reflectance and the solar reflectance. For example, aluminum particles such as aluminum flakes, or aluminum particles coated with an organic or inorganic substance on the surface (surface-treated aluminum particles) and the like can be mentioned. Examples of the organic substance in the surface-treated aluminum particles include resins, fatty acids, silane coupling agents, etc., and examples of the inorganic substance include inorganic oxides such as silica, metals other than aluminum, etc. Among them, from the viewpoint that the visible light reflectance and the solar reflectance are less likely to decrease over a long period of time, aluminum particles coated with an acrylic resin or silica are particularly preferable. Aluminum particles coated with an acrylic resin or silica are hereinafter also referred to as "specific aluminum composite particles".

[0058] 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 still more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the aluminum particles. When the total coating amount of the acrylic resin and silica is equal to or greater than the lower limit value of the above range, the aluminum particles are sufficiently protected by the acrylic resin or silica, so that the solar reflectance of the coating film is less likely to decrease over a long period. When the total coating amount of the acrylic resin and silica is equal to or less than the upper limit value of the above range, dissolution of the aluminum particles due to deterioration of the acrylic resin or generation of cracks inside the silica during the weather resistance test and dissolution of the aluminum particles by the penetrated moisture are suppressed. As a result, the solar reflectance is less likely to decrease over a long period.

[0059] When the resin composition contains specific aluminum composite particles, from the viewpoint of the balance of solar reflectance, viscosity of the resin composition, adhesion, etc., the content of the specific aluminum composite particles is preferably 10 to 35% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass with respect to the total mass of the resin composition.

[0060] 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 with respect to 100 parts by mass of the total resin in the resin composition. When referring to the content or content rate of the pigment, the content or content rate shall be the content or content rate including near-infrared absorbing pigments, near-infrared reflecting pigments, etc. described later.

[0061] (UV absorber) Examples of the UV absorber include inorganic UV absorbers and organic UV absorbers. Examples of the inorganic UV absorber include inorganic particles such as zinc oxide, titanium oxide, cerium oxide, and iron oxide; inorganic composite particles obtained by coating the surface of the inorganic particles with inorganic substances such as silica, alumina, and zirconia. 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, hydroxy-phenyltriazine-based UV absorbers such as 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (manufactured by BASF Japan Ltd., trade name: TINUVIN 479), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (manufactured by BASF Japan 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 Ltd., trade name: TINUVIN 405) are preferred.

[0062] (Near-infrared absorbing pigment and near-infrared reflecting pigment) Examples of the near-infrared absorbing pigment or near-infrared reflecting pigment include boron compounds such as lanthanum hexaboride which is a green pigment, tungsten compounds such as cesium tungstate which is a blue pigment, indium tin oxide which is a light blue pigment, stannic antimonide oxide which is a blue pigment, etc.

[0063] (Blocking improver) Examples of the blocking improver (excluding esterified cellulose resin) include silicon compounds, chlorinated polyethylene, acrylic resin beads, etc. The content of the blocking improver (excluding esterified cellulose resin) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

[0064] (Lubricant) Examples of the lubricant include various waxes such as polyolefin waxes such as polyethylene wax, fatty acid amides, fatty acid esters, paraffin waxes, polytetrafluoroethylene (PTFE) waxes, carnauba waxes, etc.

[0065] (Other additives) The resin composition of the present disclosure may contain, if necessary, additives other than those described above, such as anti-settling agents, plasticizers, dispersion stabilizers, fillers, antioxidants, antistatic agents, matting agents (such as silica and alumina), tack improvers (such as polyolefins), adhesion improvers (such as silane coupling agents), etc.

[0066] <Solvent> The resin composition of the present disclosure may be used with a solvent added thereto from the viewpoint of excellent coatability. The solvent may be any one that can dissolve or disperse the specific fluororesin, and may be appropriately selected in consideration of repellency on the substrate of the paint, transfer rate, drying property, storage stability, etc. according to the coating method. Examples of the solvent include aqueous solvents, organic solvents, etc., and one kind may be used alone or two or more kinds may be used in combination. Examples of the organic solvent include toluene, xylene, ethylbenzene, methyl ethyl ketone, ethyl acetate, etc. In gravure printing, a solvent is preferred such that the 3-zone cup viscosity of the paint is 15 to 30 seconds in order to reduce printing defects such as coating unevenness and bleeding. In inkjet printing, a higher boiling point solvent may be further added so that the ejection port of the paint does not dry.

[0067] 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, based on 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, based on the total mass of the resin composition (including the solvent). In addition, when referring to the content or content ratio of each component other than the solvent in the resin composition in the present disclosure, when the resin composition contains a solvent, the content or content ratio means the content or content ratio in the resin composition excluding the solvent. The resin composition preferably has a 3-zone cup viscosity of 15 to 30 seconds.

[0068] 〔Uses of the resin composition〕 The resin composition of the present disclosure is suitably used as a paint. In particular, when the resin composition of the present disclosure is used as a paint for application to a substrate containing a fluororesin, it is useful in that it can achieve both adhesion and blocking resistance, as well as properties such as weather resistance. Details of the substrate containing the fluororesin are as described below.

[0069] ≪Laminate≫ The laminate of the present disclosure includes a substrate and a coating film formed of the resin composition of the present disclosure. Hereinafter, specific examples of the laminate will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of a laminate according to one aspect of the present disclosure. The laminate 10 is a so-called top-print type laminate including a substrate 12 and a coating film 14 formed on the surface of the substrate 12 on the side where sunlight L is incident. FIG. 2 is a cross-sectional view showing another example of a laminate according to one aspect of the present disclosure. The laminate 10 is a so-called back-print type laminate including a substrate 12 and a coating film 14 formed on the surface of the substrate 12 opposite to the side where sunlight L is incident. In FIGS. 1 and 2, the coating film 14 is formed on only one surface of the substrate 12, but the coating film 14 may be formed on both surfaces of the substrate 12. As shown in FIGS. 1 and 2, the coating film 14 may be formed over the entire surface of the substrate 12 or may be formed partially.

[0070] <Substrate> (Fluororesin) The substrate contains a fluororesin. The fluororesin contained in the substrate is preferably a homopolymer or copolymer of fluoroolefin. Examples of the fluoroolefin include the fluoroolefins described above as the constituent units of the specific fluororesin. The fluororesin may be used alone or in combination of two or more.

[0071] Examples of the copolymer of fluoroolefin include copolymers of two or more fluoroolefins, copolymers of one or more fluoroolefins and one or more olefins or perfluoro(alkyl vinyl ether), etc. The number of carbon atoms of the fluoroolefin and olefin is preferably 2 or 3. The number of carbon atoms of the perfluoro(alkyl vinyl ether) is preferably 3 to 6.

[0072] Preferred fluororesins include vinyl fluoride polymer (hereinafter also referred to as "PVF"), vinylidene fluoride polymer (hereinafter also referred to as "PVDF"), vinylidene fluoride - hexafluoropropylene copolymer, THV, tetrafluoroethylene - propylene copolymer, tetrafluoroethylene - vinylidene fluoride - propylene copolymer, ethylene - tetrafluoroethylene copolymer (hereinafter also referred to as "ETFE"), hexafluoropropylene - tetrafluoroethylene copolymer (hereinafter also referred to as "FEP"), ethylene - hexafluoropropylene - tetrafluoroethylene copolymer (hereinafter also referred to as "EFEP"), perfluoro(alkyl vinyl ether) - tetrafluoroethylene copolymer (hereinafter also referred to as "PFA"), chlorotrifluoroethylene polymer (hereinafter also referred to as "PCTFE"), and ethylene - chlorotrifluoroethylene copolymer (hereinafter also referred to as "ECTFE"). Among the fluororesins, ETFE is particularly preferred.

[0073] 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 still more preferably 55% by mass or more. When the fluorine atom content is at least the lower limit value of the above range, the weather resistance, stain resistance, chemical resistance, and non - stickiness of the substrate are further improved, and particularly the non - stickiness and stain resistance are excellent. The fluorine atom content is determined by using a fluoride ion - selective electrode and gas chromatography in combination after combustion.

[0074] The fluororesin contained in the substrate is preferably one that can be formed into a film. As the fluororesin contained in the substrate, a polymer having excellent weather resistance and a stress at 10% elongation of 10 MPa or more is preferable. The value of the stress at 10% elongation is determined by the method specified in JIS K7127:1999 (Plastics - Test method for tensile properties - Part 3: Test conditions for films and sheets). Using dumbbell 5 as the test piece, the tension when stretched at a tensile speed of 200 mm / min is divided by the cross-sectional area of the original film to calculate. The stress at 10% elongation does not depend on the film thickness and largely depends on the composition of the fluororesin. When the stress at 10% elongation is 10 MPa or more, the snow resistance and wind pressure resistance are also excellent.

[0075] The content of the fluororesin is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and may even be 100% by mass, based on the total mass of the substrate. When the content of the fluororesin is at least the lower limit value of the above range, the weather resistance of the substrate is further excellent.

[0076] (Other components) The substrate may further contain a non-fluorine-based resin, known additives, etc. Examples of known additives include colored pigments, UV absorbers, near-infrared absorbing pigments, and near-infrared reflecting pigments. Examples of colored pigments include titanium oxide which is a white pigment, aluminum cobalt oxide which is a blue pigment, and iron oxide which is a red pigment.

[0077] Examples of UV absorbers include inorganic UV absorbers, organic UV absorbers, etc. Examples of inorganic UV absorbers include inorganic particles such as zinc oxide, titanium oxide, cerium oxide, and iron oxide; inorganic composite particles obtained by coating the surface of the inorganic particles with inorganic substances such as silica, alumina, and zirconia.

[0078] Examples of near-infrared absorbing pigments or near-infrared reflecting pigments include boron compounds such as lanthanum hexaboride, tungsten compounds such as cesium tungstate, indium tin oxide, and tin antimonide oxide.

[0079] When the coating film has a light reflection function, from the viewpoint of not inhibiting the light reflection function of the coating film, the substrate preferably has light transmissivity. 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".

[0080] The thickness of the substrate is preferably 25 to 1,000 μm, more preferably 100 to 500 μm. When the thickness of the substrate is at least the lower limit value of the above range, the mechanical strength of the substrate is excellent. When the thickness of the substrate is at most the upper limit value of the above range, the light transmissivity of the substrate is excellent. The shape of the substrate is not particularly limited, and a film is preferred.

[0081] From the viewpoint of excellent adhesion to the coating film, it is preferable that the surface of the substrate on which the coating film is formed is subjected to a surface treatment for increasing the surface tension. 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 a chemical bond is 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. Examples of the surface treatment include corona discharge treatment, metal sodium treatment, mechanical roughening treatment, excimer laser treatment, etc. From the viewpoint of high treatment speed and no need for washing after treatment, corona discharge treatment is preferred.

[0082] The surface tension of the substrate is preferably 0.035 N / m or more, more preferably 0.04 N / m or more. When the surface tension of the substrate is at least the lower limit value of the above range, the adhesion between the substrate and the coating film is further excellent. The upper limit of the surface tension of the substrate is not particularly limited, and for example, it may be 0.06 N / m.

[0083] <Coating film> The coating film is a film formed on a substrate and formed using the aforementioned resin composition. When the resin composition contains a solvent, the coating film represents the film after applying the resin composition to the substrate and removing the solvent. The coating film may be a solidified 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.

[0084] In the present disclosure, whether the film formed using the resin composition is provided over the entire surface or only a part of the surface, it falls within the scope of the "coating film". The ratio of the area of the coating film to the area of the substrate on one side of the substrate may be appropriately selected according to the purpose and the like. For example, it is 10 to 100%. More specifically, the area of the coating film may be less than 95%, less than 90%, or less than 80% with respect to the total area of one side of the substrate. Also, the area of the coating film may be 80% or more, 90% or more, or 95% or more with respect to the total area of one side of the substrate. The coating film may be formed on one side of the substrate, or may be formed on both sides of the substrate.

[0085] The coating film may be a single layer or two or more layers. The thickness of the coating film (in the case of two or more layers, the total thereof) is preferably 0.5 to 10 μm, more preferably 1 to 6 μm. When the thickness of the coating film is equal to or less than the upper limit value of the above range, the coating film can follow the deformation of the substrate such as expansion, contraction, and bending, and the coating film tends to be difficult to peel off from the substrate.

[0086] The method for forming the coating film is not particularly limited, and examples thereof include the following methods. · A method of forming a coating film by applying a resin composition onto a substrate by a known coating method such as gravure printing, screen printing, tampo printing, inkjet, brush coating, spray coating, die coating, etc., and removing the solvent when the resin composition contains a solvent. · A method of forming a coating film by applying a resin composition onto a transfer film by a known coating method, removing the solvent when the resin composition contains a solvent, and transferring the coating film on the transfer film onto a substrate by a thermal roll or the like in a substrate shape. As a method for forming a coating film, from the viewpoints of alignment accuracy, productivity, etc., gravure printing, screen printing, tampo printing, and inkjet method are preferable, and gravure printing is more preferable.

[0087] In the coating method, as a method for removing the solvent after applying the resin composition to the substrate, examples include heat drying, vacuum drying, heat vacuum drying, etc. In the case of heat drying or heat vacuum drying, the heating temperature is preferably 30 to 150°C, more preferably 60 to 120°C. The drying may be performed only once or multiple times.

[0088] When the resin composition of the present disclosure is a resin composition containing a curing agent, for example, a coating film may be formed by curing the resin composition by heating at 40 to 80°C.

[0089] On the surface of the coating film, in consideration of further forming a functional layer described later thereon, surface treatment may be performed to improve its adhesion. Examples of the surface treatment include the same treatment as the surface treatment that can be performed on the substrate.

[0090] <Layers other than the substrate and the coating film formed by the resin composition of the present disclosure> The laminate may further have a layer other than the substrate and the coating film formed by the resin composition of the present disclosure. For example, the laminate may further have a functional layer on the coating film formed by 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 may be one layer or two or more layers. In the present disclosure, the functional layer refers to a layer that imparts a desired function to the laminate. Examples of the desired function imparted to the laminate include design properties, optical properties (ultraviolet absorption, ultraviolet reflection, near-infrared absorption, near-infrared reflection, etc.), durability, etc. In the composition for forming the functional layer, as components for imparting a desired function to the laminate, examples include the pigments, UV absorbers, UV reflectors, near-infrared absorbing pigments, near-infrared reflecting pigments, curing agents, etc. described above as components of the resin composition. The functional layer tends to adhere well to the coating film. This is presumably because the esterified cellulose resin unevenly distributed on the surface of the coating film is partially dissolved or compatible with the components in the functional layer. Also, the laminate may have an adhesive layer between the substrate and the coating film formed from the resin composition of the present disclosure, or between the coating film formed from the resin composition of the present disclosure and any other layer. Examples of the adhesive layer include a layer formed by applying a silane coupling agent.

[0091] Preferred layer configurations when the laminate has a layer other than the substrate and the coating film include the following configurations. · A laminate including a substrate, the coating film, and a functional layer in this order. Optionally, an adhesive layer is provided between each layer. In this case, the functional layer may be for purposes such as design, curability, adhesion, and optical properties. · A laminate including a substrate, the coating film, a first functional layer, and optionally a second functional layer in this order. Optionally, an adhesive layer is provided between each layer. The resin composition of the present disclosure may be used for at least one selected from the group consisting of the first functional layer and the second functional layer. In this case, the first functional layer may be for purposes such as curability, adhesion, and optical properties, and the second functional layer may be for purposes such as design.

[0092] 〔Uses of the laminate〕 The use of the laminate of the present disclosure is not particularly limited. Examples of the use of the laminate include membrane structure facilities (sports facilities (pools, gymnasiums, tennis courts, soccer fields, track and field stadiums, etc.), warehouses, assembly halls, exhibition halls, horticultural facilities (greenhouses, agricultural houses, etc.), arcades, etc.) membrane materials (roof materials, exterior wall materials, skylights, waterproof sheets, curing sheets, etc.); membrane materials for screens; soundproof walls; windbreak fences; overtopping barriers; highway side walls; garage canopies; membrane materials for shopping malls; sidewalk walls; glass splash prevention films; heat-resistant sheets; water-resistant sheets; tent materials for tent warehouses; membrane materials for solar radiation control; partial roof materials for lighting; window materials to replace glass; membrane materials for flameproof partitions; curtains; membrane materials for exterior wall reinforcement; waterproof membranes; smoke-proof membranes; non-combustible transparent partitions; membrane materials for road reinforcement; interior (lighting, wall surfaces, brands, etc.); exterior (tents, signboards, etc.); automotive materials (hoods, vibration damping materials, bodies, etc.); aircraft materials; ship materials; outer casings of home appliances; inner walls of tanks, containers, etc.; filters; membrane materials for construction work, etc. In one aspect, the laminate of the present disclosure is particularly preferably used as a membrane material for membrane structure facilities, screens, signboards, or solar radiation control.

Examples

[0093] Hereinafter, embodiments of the present disclosure will be described in detail with reference to examples. 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.

[0094] The materials used in each example are as follows. [Specific fluororesin] · As the specific fluororesin 1 solution, LF200MEK (manufactured by AGC Inc., solid content: 60% by mass, solvent: methyl ethyl ketone, hydroxyl value is 31 mg(KOH) / g) was used. The resin of LF200MEK has a main chain of an alternating copolymer of fluoroethylene and hydroxyalkyl vinyl ether. · 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 is 27 mg(KOH) / g) was used. The resin of LF600 has an alternating copolymer of fluoroethylene and hydroxyalkyl vinyl ether in the main chain.

[0095] [Specific aluminum composite particles] As the specific aluminum composite particles, EMR-D5660 (trade name, manufactured by Toyo Aluminum Co., Ltd.), which is a paste-like aluminum paste containing a liquid medium, was used. This aluminum paste contains 49.5% by mass of flat particles in which the surface of flat aluminum is coated with 15% by mass of silica based on 100% by mass of aluminum, and contains 50.5% by mass of propylene glycol monomethyl ether as a solvent. The average major axis of this aluminum composite is 9 μm.

[0096] [Esterified cellulose resin] As the esterified cellulose resin, the following resins were used. · Esterified cellulose resin 1: CAB-381-2 (trade name, manufactured by Eastman Chemical Japan Co., Ltd. Glass transition point 133 °C, number average molecular weight 40,000, hydroxyl group content 1.3% by mass) · Esterified cellulose resin 2: CAB-551-0.01 (trade name, manufactured by Eastman Chemical Japan Co., Ltd. Glass transition point 85 °C, number average molecular weight 16,000, hydroxyl group content 1.5% by mass) · Esterified cellulose resin 3: CAP-482-0.5 (trade name, manufactured by Eastman Chemical Japan Co., Ltd. Glass transition point 142 °C, number average molecular weight 25,000, hydroxyl group content 2.6% by mass) Each esterified cellulose resin was dissolved in methyl ethyl ketone (MEK), and after preparing a CAB solution or a CAP solution with a solid content concentration of 20%, it was blended as a component of the paint.

[0097] [Hardener] Polyisocyanate of hexamethylene diisocyanate (trade name: Duranate A201H, manufactured by Asahi Kasei Corporation) was used. The NCO content of this curing agent is 17.2% by mass.

[0098] [UV absorber] As the UV absorber, hydroxyphenyltriazine-based Tinuvin 479 (manufactured by BASF Japan Ltd.) was used.

[0099] The evaluation methods in the examples and comparative examples are as follows.

[0100] [Evaluation method] [Adhesion] In accordance with JIS K5600-5-6:1999, 10×10 grids of 1-mm square lattice cuts were made on the coating film formed on the fluororesin film, and cellophane tape (manufactured by Nichiban Co., Ltd., trade name CT18) was adhered. When the tape was peeled off, the number of peeled squares out of 100 squares was examined, and the adhesion was evaluated according to the following evaluation criteria. This test method is also called the cross-cut cellotape (registered trademark) peel test. A: Excellent (peeling of 0 squares or more and less than 2 squares) B: Good (peeling of 2 squares or more and less than 20 squares) C: Poor (peeling of 20 squares or more) An evaluation of A or B was regarded as passing.

[0101] [Visible light transmittance, visible light reflectance] The visible light transmittance and visible light reflectance of the coating film were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100PC) in accordance with JIS R3106:1998 (Test method for transmittance, reflectance, emissivity, and solar heat gain coefficient of flat glasses). These optical properties were measured by irradiating light from the fluororesin film side. For a coating film having specific aluminum composite particles, which are a bright pigment, as the main pigment, the visible light reflectance was measured, and for a coating film having titanium oxide, aluminum cobalt oxide, or copper phthalocyanine green as the main pigment, the visible light transmittance was measured.

[0102] [Blocking test] The coated film surfaces printed on the fluororesin film were overlapped, and a metal plate was placed thereon so as to achieve a pressure of 10 N / cm 2 and the assembly was put into a constant temperature bath maintained at a constant temperature for 15 hours. Then, it was returned to 25°C, and after 1 hour, the overlapped fluororesin films were peeled off. At that time, if the coated films were partially adhered to each other, it was judged that blocking occurred. The test temperature was changed in 5°C increments from 30 to 70°C. The blocking test pass temperature refers to the highest temperature at which blocking did not occur. For example, when the blocking test pass temperature is 40°C, it means that blocking did not occur at 40°C but occurred at 45°C. When the blocking test pass temperature is 45°C or higher, it was judged as qualified by comprehensive judgment.

[0103] (Accelerated weather resistance test) Using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd., product name: 300 Sunshine Weatherometer) equipped with a carbon arc lamp in accordance with JIS K7350-4:2008, an accelerated weather resistance test was conducted for 5000 hours. The accelerated weather resistance test was carried out for both top exposure in which light is incident from the coated film side and water is sprayed on the coated film side, and back exposure in which light is incident from the substrate side and water is sprayed on the substrate side. After the accelerated weather resistance test, the adhesion of the coated film was evaluated.

[0104] [Example 1] Corona discharge treatment was performed on the surface of a 250-μm ETFE film (manufactured by AGC Inc., product name: Fluon ETFE Film 250NJ) in air at a treatment density of 150 W·min / m 2 . The surface tension of the surface subjected to the corona discharge treatment was 0.054 N / m.

[0105] A paint was prepared with the formulation shown in Table 1. A specific fluororesin 1 solution, a specific aluminum composite particle paste, and a mixed solvent of toluene / MEK = 50 / 50 (mass ratio) were mixed and stirred to obtain a silver-colored paste. The viscosity of the paint was 25 seconds with a No. 3 Zahn cup.

[0106] Subsequently, the prepared paint was gravure printed on the corona discharge treated surface of the ETFE film subjected to corona discharge treatment, and dried at 120°C for 1 minute to obtain a laminate. The thickness of the coating film was 2 μm. Table 1 shows the formulation of the paint, the content in the paint excluding the solvent, and the evaluation results.

[0107] [Examples 2 to 18] A laminate was obtained in the same manner as in Example 1 except that the formulation of the paint was changed. The viscosity of the paint was adjusted to 22 - 26 seconds in a No. 3 Zahn cup by mixing a mixed solvent of toluene / MEK = 50 / 50 (mass ratio). The thickness of the coating film after drying was 2 μm in each case. Table 1 and 2 show the formulation of the paint, the content in the paint excluding the solvent, and the evaluation results.

[0108] Among Examples 1 to 18, it was confirmed that Examples 2, 3, 5 - 7, 9 - 11, 13 - 18 using the resin composition of the present disclosure were excellent in blocking property and adhesion. On the other hand, in Examples 1, 12 where CAB was not added, and Example 4 where the content of CAB was less than 0.2 parts by mass with respect to 100 parts by mass of the specific fluororesin, the passing temperature of the blocking test was less than 45°C. In Example 8 where the content of CAB was more than 9 parts by mass with respect to 100 parts by mass of the specific fluororesin, the adhesion was insufficient. It was confirmed that Examples 9 - 11, 14, 16, 18 using a curing agent had a high passing temperature in the blocking test.

[0109] [Examples 19 to 20] Paints were prepared with the formulations shown in Table 3. The viscosity of the paint was 25 seconds in both Example 19 and Example 20 in a No. 3 Zahn cup. Subsequently, a laminate was obtained in the same manner as in Example 1.

[0110] In Examples 19 and 20, the coating film formed by the prepared paint was used as a transparent primer layer, and on top of the coating film, further UV-curable acrylic ink (ECO-UV ink manufactured by Roland) was inkjet-printed using a LEC-540 (manufactured by Roland DG Corporation), and cured by a UV irradiation mechanism built into the printing apparatus to obtain a laminate. The formulation of the paint, the content in the paint excluding the solvent, and the evaluation results are shown in Table 1. From this, it was found that this coating film is also beneficial as a primer layer during inkjet printing or as a primer layer for further forming a coating film using a paint containing a solvent. Also, gravure printing of the paint prepared in Example 2 was carried out on the coating films prepared in Examples 19 and 20, and a cross-cut cellophane tape (registered trademark) peel test was carried out on the formed coating films. As shown in Table 3, the coating film formed by the paint prepared in Example 2 was excellent in adhesion.

[0111] Note that in the coating films prepared in Examples 2 to 3, 5 to 7, 9 to 11, and 13 to 20, in the cross-cut cellophane tape (registered trademark) peel test, the coating films did not exhibit a cohesive failure mode where they adhered to both cellophane tape and a fluororesin film, and maintained good cohesive strength.

[0112]

Table 1

[0113]

Table 2

[0114]

Table 3

[0115] [Examples 21 to 24] A laminate was obtained in the same manner as in Example 1 except that the composition of the coating material was changed. The viscosity of each coating material was adjusted to 22 - 26 seconds using a No. 3 Zahn cup by mixing a mixed solvent of toluene / MEK = 50 / 50 (mass ratio). The thickness of the coating film after drying was 2 μm for all. The composition of the coating material, the content in the coating material excluding the solvent, and the evaluation results are shown in Tables 4 and 5.

[0116] In Examples 21 - 24, the qualified temperature for the blocking test was 45°C for all, and it was judged as qualified in the comprehensive judgment. Also, in the cross-cut tape (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.

[0117] [Table 4]

[0118] [Table 5]

[0119] The disclosure of Japanese Patent Application No. 2020 - 170122 is incorporated herein by reference in its entirety. 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 was specifically and individually indicated to be incorporated by reference. [Explanation of Reference Numerals]

[0120] 10 Laminate 12 Substrate 14 Coating Film L Solar Light

Claims

1. A copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group, and an esterified cellulose resin. The resin composition, wherein the content of the esterified cellulose resin is 0.2 to 5.00 parts by mass with respect to 100 parts by mass of the copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group.

2. The resin composition according to claim 1, wherein the hydroxyl group content of the esterified cellulose resin is 0.1 to 10% by mass.

3. The resin composition according to claim 1 or 2, wherein the esterified cellulose resin contains at least one selected from the group consisting of cellulose acetate butyrate resin and cellulose acetate propionate resin.

4. The resin composition according to any one of claims 1 to 3, wherein the fluoroolefin contains at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluorobutene-1, perfluorohexene-1, perfluorononene-1, and (perfluoroalkyl)ethylene.

5. The resin composition according to any one of claims 1 to 4, wherein the monomer having a hydroxyl group contains at least one selected from the group consisting of allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl (meth)acrylate, hydroxyalkyl vinyl carboxylate, and hydroxyalkyl allyl carboxylate.

6. Does not contain a curing agent, or Contains a curing agent, and the molar ratio of the curable group in the curing agent to the hydroxyl group in the copolymer having a fluoroolefin unit and a monomer unit having a hydroxyl group is 0.5 or less. The resin composition according to any one of claims 1 to 5.

7. The resin composition according to any one of claims 1 to 6, which is a paint for applying to a substrate containing a fluororesin.

8. A laminate comprising a substrate and a coating film formed of the resin composition according to any one of claims 1 to 6.

9. The laminate according to claim 8, wherein the substrate contains a fluororesin.

10. The laminate according to claim 9, wherein the 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.

11. The laminate according to any one of claims 8 to 10, which is a film material for a membrane structure facility, a screen, a signboard, or solar radiation control.

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