Thermosetting resin composition, film, and article including the film

Abstract

To provide a thermosetting resin composition that can strike a balance between the moldability and chemical resistance of a film.SOLUTION: A thermosetting resin composition includes: (A) a (meth)acrylic resin including a hydroxy group; (B) a polyol compound different from the component (A); and (C) a polyisocyanate compound, wherein at least one of the component (A), the component (B) and the component (C) has a heterocyclic polycyclic skeleton.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, a film, and an article comprising the film. [Background technology]

[0002] Films are generally applied to the surfaces of automobile interior parts, lifestyle-related parts, furniture and building materials-related parts, etc. for protection and decoration of the parts. Films and membranes for protecting such articles are often formed from resin compositions, etc., and various resin compositions for film formation have been developed.

[0003] Patent Document 1 describes a polyurethane that is a reaction product of an acrylic polyol and an isocyanate, and a polyurethane that contains a chain extension portion formed by an anhydrosugar alcohol, and describes that the polyurethane is used as a coating material, etc. Furthermore, Patent Document 2 describes a coating composition characterized by containing isosorbide di(meth)acrylate, a hydroxyl group-containing resin, and an isocyanate group-containing compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2017-519052 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-246351 Summary of the Invention [Problem to be solved by the invention]

[0005] As mentioned above, various parts, such as automotive interior parts, often have complex shapes with three-dimensional curves. Therefore, films to be attached to such parts must have the property (formability) to easily stretch and fit the curved surface.

[0006] Furthermore, the above-mentioned automobile interior parts and lifestyle-related parts are products that are closely related to people's lives, and therefore, when they are exposed to various everyday products such as sunscreens and insect repellents, they must be resistant to these chemicals (chemical resistance).

[0007] However, the present inventors have found that there is room for improvement in the conventional techniques with respect to formability and chemical resistance when attaching a film to a molded article.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermosetting resin composition that can achieve both moldability and chemical resistance when formed into a film. [Means for solving the problem]

[0009] An object of the present invention is to provide a thermosetting resin composition that can achieve both film formability and chemical resistance.

[0010] According to the present invention, (A) a (meth)acrylic resin containing a hydroxy group; (B) a polyol compound different from the component (A); (C) a polyisocyanate compound, There is provided a thermosetting resin composition in which at least one of the components (A), (B) and (C) has a heteropolycyclic skeleton.

[0011] Furthermore, according to the present invention, there is provided a film formed from the above-mentioned thermosetting resin composition.

[0012] The present invention also provides an article comprising the above film. [Effects of the Invention]

[0013] According to the present invention, there is provided a thermosetting resin composition that can achieve both film formability and chemical resistance. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a diagram schematically illustrating an example of a film and a shaped product (molded product) according to the present embodiment. [Figure 2] 1 is a diagram schematically illustrating an example of a film and a shaped product (molded product) according to the present embodiment. [Figure 3] 1 is a diagram schematically illustrating an example of a film and a shaped product (molded product) according to the present embodiment. [Figure 4] 1A to 1C are diagrams schematically illustrating the process of attaching the film of the present embodiment to an article by an out-molding method. [Figure 5] FIG. 2 is a diagram schematically showing the shape of a molded body used in the moldability evaluation of the examples. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described in detail.

[0016] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups having no substituents and groups having a substituent. For example, the term "alkyl group" encompasses not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups). In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In this specification, the term "film" encompasses a coating film formed from the thermosetting resin in this embodiment, a film alone, and a film attached to a functional layer, a substrate layer, a shaped object (article), etc.

[0017] <Thermosetting resin composition> The thermosetting resin composition of the present embodiment is (A) a (meth)acrylic resin containing a hydroxy group; (B) a polyol compound different from the component (A); (C) a polyisocyanate compound; Includes: At least one of the components (A), (B) and (C) has a heteropolycyclic skeleton.

[0018] By using the thermosetting resin composition of this embodiment, a film that can achieve both moldability and chemical resistance can be obtained. Although the details of this mechanism are not clear, it can be explained as follows. It should be noted that the scope of the present invention is not limited by the following explanation.

[0019] The thermosetting resin composition of the present embodiment can be cured to form a film that can be attached to a shaped article (such as a molded product), for example. According to the findings of the present inventors, it has become clear that when the glass transition temperature of a film formed from a thermosetting resin composition is high, the film is less likely to break or peel when being attached to a molded body or after being attached to a molded body. In this embodiment, by introducing a heteropolycyclic skeleton into any of the components contained in the thermosetting resin composition that forms the film, it is possible to increase the glass transition temperature of the film. Furthermore, it is believed that the formation of hydrogen bonds between oxygen, nitrogen, sulfur, etc. in the heteropolycyclic skeleton and other components of the thermosetting resin composition gives the film toughness, making it less likely to break or peel when attached to a molded body or after being attached to a molded body. Furthermore, according to the findings of the present inventors, it has become clear that increasing the glass transition temperature of the film increases the chemical resistance. It is believed that by increasing the glass transition temperature when the film is formed in this way, it is possible to achieve both formability and chemical resistance when the film is attached to an article.

[0020] A film formed using the thermosetting resin composition of this embodiment can be attached to a molded article by heat stretching, etc. The advantages of this will be explained below. When attaching a film to a molded body, it is generally attached via an adhesive sheet. There are various types of adhesive sheets, but the ability to heat them allows for the use of heat-sealed adhesive sheets, which has the advantage of broadening the range of adhesive sheet options. Furthermore, when attaching a laminated film with a base layer (described below) to a molded body, depending on the material, the base layer is difficult to stretch at room temperature, so if it can be softened by heating, the laminated film can be neatly attached to the molded body.

[0021] In the thermosetting resin composition of this embodiment, at least one of the (A) (meth)acrylic resin, (B) polyol compound, and (C) polyisocyanate compound described below has a heteropolycyclic skeleton. That is, when component (A) has a heteropolycyclic skeleton, when component (B) has a heteropolycyclic skeleton, or when component (C) has a heteropolycyclic skeleton, the heteropolycyclic skeleton may be contained in only one component among component (A), component (B), and component (C), or may be contained in two or more components.

[0022] A heteropolycyclic skeleton is a skeleton containing multiple closed rings composed of carbon and atoms other than carbon (heteroatoms). Examples of the ring in the heteropolycyclic skeleton include three- to eight-membered rings. The ring is preferably a five- or six-membered ring, more preferably a five-membered ring. An example of a five-membered ring structure is tetrahydrofuran, and an example of a six-membered ring structure is pyridine. The heteropolycyclic skeleton may have two or more rings, but is preferably a bicyclic or tricyclic skeleton, which can impart appropriate toughness to the film.

[0023] Examples of atoms other than carbon (heteroatoms) in the heteropolycyclic skeleton include oxygen, nitrogen, sulfur, etc., and oxygen is preferred. The heteroatoms in the heteropolycyclic skeleton can form hydrogen bonds with the other components (A), (B), and (C) in the thermosetting resin composition, which is thought to impart toughness to the film and make it less susceptible to breakage or peeling after being attached to a molded article.

[0024] When a heteropolycyclic skeleton is introduced into (A) the (meth)acrylic resin, (B) the polyol compound, or (C) the polyisocyanate compound, a chemical bond such as a covalent bond can be formed between the heteropolycyclic skeleton and each component by adding the heteropolycyclic compound when synthesizing component (A), component (B), or component (C). Commercially available products of the above components into which a heteropolycyclic skeleton has been introduced may also be used. Furthermore, the heteropolycyclic compound may be component (A), component (B), or component (C) itself.

[0025] The heteropolycyclic skeleton is preferably a skeleton derived from isosorbide represented by the following formula (1). Isosorbide has hydrogen bonding properties due to its chemical structure, and therefore, when at least one of components (A), (B), and (C) in the thermosetting resin composition contains a skeleton derived from isosorbide, toughness is more effectively imparted to the film, making it possible to prevent breakage or peeling during or after application to a molded body.

[0026] [ka]

[0027] When the heteropolycyclic skeleton is derived from isosorbide, the content of the structural unit containing the heteropolycyclic skeleton in the thermosetting resin composition is preferably 3% by mass or more, more preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more, relative to 100% by mass of the total solid content of the thermosetting resin composition. Also, this content is preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 21% by mass or less. By setting the content ratio of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition within the above range, it is believed that toughness can be more effectively imparted to the film, and breakage and peeling of the film after it is attached to a molded article can be further suppressed.

[0028] When the heteropolycyclic skeleton is a skeleton derived from isosorbide, the content ratio of the structural unit containing the heteropolycyclic skeleton in the thermosetting resin composition is expressed as follows. The content ratio of the molecular weight corresponding to the portion obtained by removing hydrogen atoms from two hydroxy groups bonded to a five-membered ring in isosorbide represented by the following formula (1) is defined as the content ratio (mass%) of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition.

[0029] [ka]

[0030] ((A) (meth)acrylic resin) The thermosetting resin composition in this embodiment contains (A) a (meth)acrylic resin. The (meth)acrylic resin (A) refers to a resin (polymer) containing structural units derived from (meth)acrylic acid and / or (meth)acrylic acid ester monomers. That is, the (meth)acrylic resin (A) may also contain structural units derived from non-(meth)acrylic monomers. However, from the viewpoint of fully obtaining the effects derived from the (meth)acrylic structure, the (meth)acrylic resin (A) preferably contains structural units derived from (meth)acrylic acid and / or (meth)acrylic acid ester monomers in an amount of 50% by mass or more (more preferably 60% by mass or more of the total structural units) relative to 100% by mass of all structural units of the (meth)acrylic resin (A).

[0031] From another perspective, the (meth)acrylic resin (A) may have at least one partial structure selected from the group consisting of polycaprolactone, polycaprolactam, polycarbonate, polyester, and polyether. These chemical structures have moderate flexibility and elasticity, and therefore can enhance the flexibility and elasticity of the film. Incidentally, it is preferable that these partial structures are present in the side chains of the (meth)acrylic resin (A).

[0032] The (meth)acrylic resin (A) in this embodiment preferably contains, as a structural unit, one or more (meth)acrylic monomers selected from the group consisting of the following (i) to (iv): The (meth)acrylic monomer is preferably one represented by the general formula CH2=CR-COO-R'. Here, R is a hydrogen atom or a methyl group, and R' is a hydrogen atom or a monovalent organic group. The monovalent organic group R' is preferably an alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group, and these groups may further have a substituent. In addition, two or more kinds of (meth)acrylic monomers may be selected from those corresponding to (i), for example.

[0033] (i) A monomer having the general formula CH2=CR-COO-R', where R' is a monovalent organic group, which is an alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Among these, alkyl groups with fewer carbon atoms in R' have higher glass transition temperatures (°C), while alkyl groups with more carbon atoms in R' have lower glass transition temperatures (°C). Depending on the desired glass transition temperature (°C) of the (meth)acrylic resin (A), monomers with alkyl groups with different numbers of carbon atoms in R' can be used in combination.

[0034] When the (meth)acrylic resin (A) contains a structural unit derived from this monomer, the content thereof is preferably 0.5 to 98 mass%, more preferably 0.7 to 95 mass%, and even more preferably 1 to 93 mass%, relative to 100 mass% of all structural units in the (meth)acrylic resin (A).

[0035] (ii) A monomer in which the monovalent organic group of R' in the general formula CH2=CR-COO-R' is substituted with a polar group such as a hydroxy group or an amino group. Specific examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate. When the (meth)acrylic resin (A) contains a structural unit derived from this monomer, the content thereof is preferably 1 to 40 mass %, more preferably 5 to 30 mass %, relative to 100 mass % of all structural units in the (meth)acrylic resin (A).

[0036] (iii) A monomer in which R' in the general formula CH2=CR-COO-R' contains at least one partial structure selected from the group consisting of polycaprolactone, polycaprolactam, polycarbonate, polyester, and polyether. Specific examples include the "Placcel F" series manufactured by Daicel Corporation, methoxypolyethylene glycol mono(meth)acrylate having an ethylene oxide addition mole number of 3 to 20, polypropylene glycol mono(meth)acrylate, and 2-(2-ethoxyethoxy)ethyl acrylate. Resins containing structural units derived from the monomer (iii) are considered to be particularly preferable in terms of improving the flexibility of the film. When the (meth)acrylic resin (A) contains a structural unit derived from this monomer, the content thereof is preferably 1 to 60 mass %, more preferably 5 to 50 mass %, relative to 100 mass % of all structural units in the (meth)acrylic resin (A).

[0037] (iv) Monomers of the general formula CH2=CR-COO-R', where R' is a hydrogen atom. A specific example of this is (meth)acrylic acid. When the (meth)acrylic resin (A) contains a structural unit derived from this monomer, the content thereof is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, relative to 100 mass % of all structural units in the (meth)acrylic resin (A).

[0038] The (meth)acrylic resin (A) in this embodiment may contain a structural unit derived from a (meth)acrylamide monomer as a structural unit not derived from either (meth)acrylic acid or a (meth)acrylic acid ester monomer. Specific examples of (meth)acrylamides include dimethyl(meth)acrylamide, (meth)acryloylmorpholine, hydroxyethyl(meth)acrylamide, diethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, and dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt. When the (meth)acrylic resin (A) contains a structural unit derived from a (meth)acrylamide monomer, the content thereof is, for example, 0.1 to 50 mass%, preferably 0.1 to 20 mass%, and more preferably 1 to 10 mass%, relative to 100 mass% of all structural units in the (meth)acrylic resin (A).

[0039] The (meth)acrylic resin (A) in the thermosetting resin composition of this embodiment has a hydroxy group, and the hydroxy group of the (meth)acrylic resin (A) can react with an isocyanate group of the polyisocyanate compound (C) described below to form a crosslinked structure.

[0040] It is known that the hydroxyl value is used as a method for quantifying the hydroxyl groups contained in the (meth)acrylic resin (A). In this embodiment, the hydroxyl value of the (meth)acrylic resin (A) is preferably 20 mgKOH / g or more, more preferably 30 to 150 mgKOH / g, and even more preferably 30 to 120 mgKOH / g. By setting the value within this range, the (C) polyisocyanate compound and (A) (meth)acrylic resin react appropriately, and the crosslinked structure is appropriately controlled, which allows the glass transition temperature of the film to be increased while maintaining the film's flexibility and elasticity. Incidentally, the hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid that has bonded with the hydroxyl groups when 1 g of a sample is acetylated. Specifically, it can be measured and calculated according to the method specified in "7.1 Neutralization titration method" of JIS K 0070 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products."

[0041] The weight average molecular weight (Mw) of the (A) (meth)acrylic resin is preferably 5,000 to 50,000, more preferably 7,000 to 40,000, even more preferably 10,000 to 30,000, and particularly preferably 15,000 to 25,000. By setting the content at or above this lower limit, the adhesion of the film to the molded article can be improved, while by setting the content at or below this upper limit, the generation of bubbles in the film can be suppressed, resulting in a better film. The weight average molecular weight (Mw) of the (meth)acrylic resin (A) can be adjusted by adjusting conditions such as the polymerization reaction time, reaction temperature, and amount of polymerization initiator used. The weight average molecular weight Mw can be measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0042] The glass transition temperature (°C) of the (meth)acrylic resin (A) is preferably from 1 to 100°C, and more preferably from 30 to 100°C. By setting the content within the above range, it becomes easier to adjust the glass transition temperature of the film, and also by setting the content within the above range, the compatibility between the (A) (meth)acrylic resin and the (C) polyisocyanate compound and the like is improved, and the handling during mixing or preparation of the thermosetting resin composition can be improved.

[0043] The glass transition temperature (°C) of the (meth)acrylic resin (A) can be calculated from the compounding ratio of the monomers used using the following Fox equation. 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+(W3 / Tg3)+···+(W n / Tg n ) [Wherein, Tg is the glass transition temperature of the resin (K), W1, W2, W3...W n are the mass fractions of the respective monomers, Tg1, Tg2, Tg3, Tg n indicates the glass transition temperature (K) of a homopolymer composed of monomers corresponding to the mass fraction of each monomer.] For monomers whose glass transition temperatures are unknown, such as special monomers and polyfunctional monomers, the glass transition temperature can be determined using only monomers whose glass transition temperatures are known.

[0044] The content of the (meth)acrylic resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, relative to 100% by mass of the total solid content of the thermosetting resin composition. By adjusting the content to the above range, the glass transition temperature when formed into a film can be set within an appropriate range, and the formability and chemical resistance of the film can be further improved. Furthermore, when the (meth)acrylic resin (A) has a heteropolycyclic skeleton, the content of the (meth)acrylic resin (A) is preferably 10% by mass or more, preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, relative to 100% by mass of the total solid content of the thermosetting resin composition. By setting the thickness within the above range, it is believed that the film is given an appropriate toughness, and is less likely to break or peel off after being attached to a molded article.

[0045] The method for producing the (meth)acrylic resin (A) is not particularly limited, and known methods can be appropriately applied. For example, production by polymerization reaction is preferred, and production by radical polymerization is more preferred. Furthermore, the polymerization may be any known method such as solution polymerization, suspension polymerization, or emulsion polymerization. Of these, solution polymerization is preferred from the viewpoint of precise control of polymerization.

[0046] Known initiators for radical polymerization can be used. Examples include azo initiators such as 1,1-azobis-1-cyclohexanecarbonitrile, azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2-methylpropionitrile), and 2,2-azobis(2,4-dimethylvaleronitrile); peroxide initiators such as benzoyl peroxide, t-butyl peroxyoctanoate, diisobutyl peroxide, di(2-ethylhexyl) peroxypivalate, decanoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxybenzoate; and redox initiators combining an oxidizing agent and a reducing agent, such as hydrogen peroxide and an iron(II) salt, or a persulfate and sodium hydrogen sulfite. These initiators can be used alone or in combination of two or more. The amount of the polymerization initiator to be added is not particularly limited, but is preferably 0.001 to 10 parts by mass when the total mixed solution of the monomers to be polymerized is 100 parts by mass.

[0047] In addition, during the polymerization reaction, known chain transfer agents, polymerization inhibitors, molecular weight modifiers, etc. may be used as appropriate. Furthermore, the polymerization reaction may be carried out in one stage or in two or more stages. The temperature of the polymerization reaction is not particularly limited, but is appropriately adjusted taking into consideration the 10-hour half-life temperature of the polymerization initiator. It is typically within the range of 50 to 200°C, preferably 70 to 150°C.

[0048] ((B) Polyol Compound) The thermosetting resin composition of this embodiment contains (B) a polyol compound, i.e., a compound having two or more hydroxy groups in one molecule. The hydroxy groups of the polyol compound can react with the isocyanate groups of (C) a polyisocyanate compound (described later), thereby curing the film. The number of hydroxy groups that the (B) polyol compound has in one molecule is usually 2 or more, preferably 2 to 6, and more preferably 2 to 4. The (meth)acrylic resin (A) described above includes a hydroxy group and therefore corresponds to a polyol. However, the (B) polyol compound in this embodiment excludes the (meth)acrylic resin (A) described above.

[0049] The (B) polyol compound preferably contains at least one polyol selected from the group consisting of polycaprolactone polyol, polycarbonate polyol, polyester polyol, and polyether polyol. These polyols have a moderately flexible and elastic chemical structure. This can further enhance the flexibility and elasticity of the film. This is therefore desirable in terms of absorbing external forces.

[0050] The polycaprolactone polyol can be any compound having a caprolactone ring-open structure and two or more hydroxy groups in one molecule, and specific examples include polyols represented by any of the following general formulas (P-1) to (P-3).

[0051] [ka]

[0052] In general formula (P-1), R represents a divalent organic group. Examples of the divalent organic group include linear alkylene groups such as -CH- and -CH-, branched alkylene groups such as -CH-C(CH)-CH-, and ether-containing groups such as -CH-O-CH-. Each X is independently a linear or branched alkylene group, and the alkylene group preferably has 3 to 7 carbon atoms, and more preferably 4 to 6 carbon atoms. m and n each independently represent an integer of 1 or greater. Preferably, m and n each represent an integer of 2 to 20. Furthermore, the sum of m and n is preferably 4 to 35.

[0053] In general formula (P-2), R represents a trivalent organic group. Examples of the trivalent organic group include a structure in which three hydrogen atoms have been removed from a linear or branched alkane, or a structure in which three hydrogen atoms have been removed from a trialcohol having an isocyanuric skeleton. Each X is independently a linear or branched alkylene group, and the alkylene group preferably has 3 to 7 carbon atoms, and more preferably 4 to 6 carbon atoms. l, m, and n each independently represent an integer of 1 or greater. l, m, and n are preferably each an integer of 2 to 20. The sum of l, m, and n is preferably 3 to 40.

[0054] In general formula (P-3), R represents a tetravalent organic group. Examples of the tetravalent organic group include a structure in which four hydrogen atoms have been removed from a linear or branched alkane. Each X is independently a linear or branched alkylene group, and the alkylene group preferably has 3 to 7 carbon atoms, and more preferably 4 to 6 carbon atoms. k, l, m, and n each independently represent an integer of 1 or greater. Preferably, k, l, m, and n each represent an integer of 2 to 20. Furthermore, the sum of k, l, m, and n is preferably 4 to 50.

[0055] As commercially available polycaprolactone polyols, for example, those under the trade names of Daicel Corporation's PLACCEL 200 series, PLACCEL 300 series, and PLACCEL 400 series are available.

[0056] The polycarbonate polyol can be used without any particular limitation as long as it is a compound having a carbonate group represented by -O-(C=O)-O- and two or more hydroxy groups in one molecule. Polycarbonate polyols can be obtained by reacting one or more polyol raw materials (polyhydric alcohols) with a carbonate ester or phosgene. The polyol raw material is not particularly limited, and examples thereof include aliphatic polyols, polyols having an alicyclic structure, aromatic polyols, etc. In the present embodiment, from the viewpoint of flexibility of the film, aliphatic polyols not having an alicyclic structure are preferred. Examples of carbonate esters include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate. Among these, aliphatic carbonate esters are preferred in terms of availability and ease of production, and dimethyl carbonate is particularly preferred. Among polycarbonate polyols, it is particularly preferable to contain polycarbonate diol, which can increase the flexibility and elasticity of the film and particularly suppress the occurrence of cracks during film formation.

[0057] The polyester polyol can be any compound having an ester group (-COO- or -OCO-) and two or more hydroxy groups in one molecule, without any particular limitation. The polyester polyol can be obtained by reacting one or more kinds of polyol raw materials (polyhydric alcohols) with an ester-forming compound such as a polycarboxylic acid or its ester, anhydride, or halide. The polyol raw material is not particularly limited, and examples thereof include the same polyol raw materials as those for the polycarbonate polyol described above. The ester-forming compound, such as polycarboxylic acid or its ester, anhydride, or halide, is not particularly limited, and examples thereof include polycarboxylic acids such as aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and tricarboxylic acid compounds, as well as acid anhydrides, halides, and lower ester compounds of these polycarboxylic acids.

[0058] The polyether polyol can be used without any particular limitation as long as it is a compound having an ether bond (—O—) and two or more hydroxy groups in one molecule. Specific examples of the compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers and block copolymers of ethylene oxide and propylene oxide, and ethylene oxide and butylene oxide.

[0059] In this embodiment, the polyol may be a compound that corresponds to two or more of polycaprolactone polyol, polycarbonate polyol, polyester polyol, and polyether polyol. For example, the polyol may be a polyether polyester polyol having an ether bond and an ester bond.

[0060] An example of a case where the (B) polyol compound has a heteropolycyclic skeleton is when the (B) polyol compound is the above-mentioned isosorbide itself. Isosorbide is classified as a polyol because it has two hydroxy groups. In addition to the above, when the polyol compound (B) has a heteropolycyclic skeleton, a commercially available compound in which isosorbide is bonded to a polycarbonate diol can be used. An example of such a commercially available compound is BENEBiOL HS0840B (trade name) manufactured by Mitsubishi Chemical Corporation. Further examples of the (B) polyol compound having a heteropolycyclic skeleton include compounds in which the hydroxy group of isosorbide has been modified with alkylene glycol, compounds in which the hydroxy group of isosorbide has been modified with ε-caprolactone, compounds in which the hydroxy group of isosorbide has been modified with lactide, compounds in which the hydroxy group of isosorbide has been modified with a polyfunctional isocyanate, and polyester polyols having an isosorbide skeleton (specifically, those described in JP 2013-142128 A).

[0061] The molecular weight of the (B) polyol compound, for example, in catalog values, is preferably 50 to 3000, more preferably 100 to 2000. By adjusting the molecular weight to an appropriate level, the flexibility and elasticity of the film can be further improved. The hydroxyl value of the (B) polyol compound is, for example, a catalog value of preferably 50 to 900 mgKOH / g, more preferably 55 to 800 mgKOH / g. By adjusting the amount of hydroxyl groups to a suitable level, the crosslinked structure formed by the reaction with the (C) isocyanate compound (described later) can be appropriately controlled, which is expected to improve the film elongation and formability.

[0062] The content of the (B) polyol compound is usually 10 to 60 mass%, preferably 20 to 50 mass%, and more preferably 25 to 40 mass%, relative to 100 mass% of the total solids content of the thermosetting resin composition. The amount of the (B) polyol compound is usually 30 to 150 mass parts, preferably 40 to 140 mass parts, and more preferably 50 to 120 mass parts, relative to 100 mass parts of the (A) (meth)acrylic resin. By using this range, it is possible to obtain sufficient performance derived from the (B) polyol compound while also achieving a good balance with other components. Furthermore, when the (B) polyol compound has a heteropolycyclic skeleton, the content of the (B) polyol compound is preferably 3% by mass or more, preferably 5% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less, relative to 100% by mass of the total solid content of the thermosetting resin composition. By setting the thickness within the above range, it is believed that the film is given an appropriate toughness, and is less likely to break or peel off after being attached to a molded article.

[0063] When the (B) polyol compound has a heteropolycyclic skeleton, the (B) polyol compound may further contain a (B) polyol compound other than the (B) polyol compound having a heteropolycyclic skeleton. The molecular weight of the (B) polyol compound other than the (B) polyol compound having a heteropolycyclic skeleton is preferably not more than 5000, more preferably not more than 3000, and even more preferably not more than 2000. There is no particular lower limit to this molecular weight, but the lower limit is, for example, 50, preferably 100, and more preferably 200. By further containing the polyol compound (B) having a molecular weight within the above range, the flexibility of the film can be further increased.

[0064] When the thermosetting resin composition contains a (B) polyol compound other than a (B) polyol compound having a heteropolycyclic skeleton, the content of the (B) polyol compound other than a (B) polyol compound having a heteropolycyclic skeleton is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, relative to 100% by mass of the total solids content of the thermosetting resin composition. The content of the (B) polyol compounds other than the (B) polyol compound having a heteropolycyclic skeleton is preferably 90 parts by mass or more, more preferably 100 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, per 100 parts by mass of the (B) polyol compound having a heteropolycyclic skeleton. By adjusting the content within the above range, the flexibility of the film can be adjusted appropriately, and for example, the formability and shape retention can be further improved.

[0065] ((C) Polyisocyanate Compound) The thermosetting resin composition of the present embodiment contains a polyisocyanate compound. The isocyanate group of the (C) polyisocyanate compound can react with the hydroxy group of the (A) (meth)acrylic resin and / or the (B) polyol compound to form a crosslinked structure.

[0066] The polyisocyanate compound (C) is polyfunctional, i.e., a compound having two or more isocyanate groups (including isocyanate groups protected with leaving groups) in one molecule. The number of functional groups in the polyisocyanate compound (C) is preferably 2 to 6 per molecule, more preferably 2 to 4 per molecule.

[0067] Examples of the (C) polyisocyanate compound include aliphatic diisocyanates such as lysine isocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate, cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-(or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanatomethyl)cyclohexane, and tri- or higher functional isocyanates such as lysine triisocyanate. Isocyanurate and biuret adducts, which are polymers of isocyanate compounds, and adducts of isocyanate compounds with polyhydric alcohols or low-molecular-weight polyester resins can also be used as the (C) polyisocyanate compound.

[0068] Known polyisocyanate compounds include biuret type, isocyanurate type, adduct type, etc. In the present embodiment, any of these can be used, but it is preferable to use an isocyanurate type polyisocyanate compound, i.e., a polyisocyanate compound having a cyclic skeleton of isocyanuric acid.

[0069] The polyisocyanate compound (C) may be a so-called blocked isocyanate. In other words, some or all of the isocyanate groups of the polyisocyanate compound (C) may be in the form of blocked isocyanate groups blocked with protecting groups. For example, blocked isocyanate groups are formed by blocking the isocyanate groups with active hydrogen compounds such as alcohols, phenols, lactams, oximes, and active methylenes. In particular, when the thermosetting resin composition of this embodiment is a one-component system, a polyisocyanate compound having blocked isocyanate groups is preferred from the viewpoint of storage stability (stability over time).

[0070] As a commercially available product of the (C) polyisocyanate compound, for example, the Duranate (trade name) series manufactured by Asahi Kasei Corporation can be used.

[0071] The content of the polyisocyanate compound (C) is usually 5 to 60 mass %, preferably 10 to 50 mass %, based on 100 mass % of the total solid content of the thermosetting resin composition, and the amount of the polyisocyanate compound (C) is usually 20 to 300 mass parts, preferably 30 to 200 mass parts, based on 100 mass parts of the (meth)acrylic resin. By setting the content of the (C) polyisocyanate compound at or above the lower limit, the crosslinking between the acrylic resin and the (C) polyisocyanate compound is made denser, resulting in a stronger film with improved chemical resistance. Also, by setting the content of the (C) polyisocyanate compound at or below the upper limit, the reaction of unreacted isocyanate groups with moisture in the air after the film is formed is suppressed, leading to higher film quality. Furthermore, when the (C) polyisocyanate compound has a heteropolycyclic skeleton, the content of the (C) polyisocyanate compound is preferably 5% by mass or more, preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, relative to 100% by mass of the total solids content of the thermosetting resin composition. By setting the thickness within the above range, it is believed that the film is given an appropriate toughness, and breakage or peeling is less likely to occur during or after application to a molded article.

[0072] From another perspective, it is preferable to set the molar ratio of the hydroxy groups in the (A) (meth)acrylic resin or the (B) polyol compound to the isocyanate groups (including blocked isocyanate groups) in the (C) polyisocyanate compound to an appropriate value. This molar ratio is also called the "equivalent ratio." Specifically, the molar ratio (NCO / OH) of the isocyanate groups in the (C) polyisocyanate compound to the hydroxy groups in the (A) (meth)acrylic resin or the (B) polyol compound is preferably 0.5 to 1.5, more preferably 0.6 to 1.1. By setting the molar ratio within the above range, the crosslinked structure between the components can be controlled, further improving the formability and shape retention of the film, and further improving chemical resistance.

[0073] (Leveling agent) The thermosetting resin composition of the present embodiment may contain a leveling agent, if necessary. As the leveling agent, known leveling agents can be appropriately used. Examples include silicone resins such as polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, polyether-modified methylalkylpolysiloxane copolymers, and aralkyl-modified methylalkylpolysiloxane copolymers. Other examples include acetylene glycol-based surfactants. When a leveling agent is used, only one type may be used, or two or more types may be used.

[0074] When the thermosetting resin composition contains a leveling agent, the content thereof is usually 0.05 to 15 mass %, and preferably 0.1 to 10 mass %, based on the total mass of the thermosetting resin composition.

[0075] (Urethanization catalyst) The thermosetting resin composition of the present embodiment may contain a urethanization catalyst as needed. As the urethanization catalyst, known catalysts can be appropriately used, and examples thereof include organometallic catalysts including stannous acetate, stannous butyrate, stannous laurate, stannous octoate, stannous oleate, bismuth octoate, cobalt naphthenate, zinc naphthenate, cadmium naphthenate, dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, and dimethyltin dineodecanoate.

[0076] When the thermosetting resin composition contains a urethane catalyst, the content thereof is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total mass of the thermosetting resin composition.

[0077] (Other ingredients) The thermosetting resin composition of the present embodiment may further contain other components as needed, such as a curing accelerator (such as a curing catalyst) other than the urethanization catalyst, an ultraviolet curable resin, a photoinitiator, an ultraviolet absorber, a light stabilizer, a dispersant, and an antioxidant.

[0078] (solvent) The thermosetting resin composition of this embodiment is typically used in a state where each component is dissolved or dispersed in a solvent. In one embodiment, the solvent is an organic solvent, and examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and isobutanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.

[0079] The amount of solvent used is not particularly limited, but can be used in an amount such that the concentration of solids (non-volatile components) is, for example, 5 to 90 mass %, preferably 10 to 85 mass %.

[0080] (Ratio of each ingredient, etc.) By appropriately adjusting the ratio of the components in the thermosetting resin composition of this embodiment, the physical properties (flexibility, etc.) of the film formed can be improved, and a suitable film can be obtained.

[0081] (Characteristics of thermosetting resin composition) The properties of the thermosetting resin composition of this embodiment will be described in detail below.

[0082] When a film is formed using the thermosetting resin composition of this embodiment, the upper limit of the glass transition temperature of the film is preferably 140° C. or lower, more preferably 135° C. or lower, and even more preferably 130° C. or lower. The lower limit of the glass transition temperature of the film is preferably 35° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, and particularly preferably 75° C. or higher. When the glass transition temperature of the film is within the above range, the film becomes more easily stretchable, and the formability when attached to a molded article and the shape retention during and after attachment to a molded article are further improved.

[0083] The glass transition temperature of the film is measured as follows. First, the thermosetting resin composition is applied to a polypropylene substrate using an applicator at a coating thickness of 10 mils and allowed to stand for 1 minute. After standing, the coated substrate is cured at 80°C for 5 days. The substrate is then allowed to stand for 1 week at 25°C and 50% relative humidity, and the cured film is peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. The resulting film is then cut into test pieces measuring 5 mm wide and 50 mm long.

[0084] Using the obtained test piece, the maximum value of loss tangent tanδ when dynamic viscoelasticity was measured at a frequency of 1.0 Hz and a temperature range of -40 to 160°C max is the glass transition temperature (°C) of the film.

[0085] When a film is formed using the thermosetting resin composition of this embodiment, the upper limit of the inter-crosslink molecular weight of the film is preferably 15,000 or less, more preferably 13,000 or less, and even more preferably 11,000 or less. The lower limit of the inter-crosslink molecular weight of the film is preferably 500 or more, more preferably 550 or more, even more preferably 600 or more, particularly preferably 1,000 or more, and especially preferably 1,500 or more. By ensuring that the molecular weight between crosslinks of the film is equal to or greater than the above lower limit, the crosslinks formed between the hydroxyl groups of the (A) (meth)acrylic resin or (B) polyol compound and the isocyanate groups of the (C) isocyanate compound are appropriately dense, thereby reducing the gaps through which chemicals can penetrate, making it more difficult for chemicals to penetrate the film, and further improving the chemical resistance of the film. Furthermore, by having the molecular weight between crosslinks of the film be equal to or less than the above upper limit, the crosslinks become appropriately sparse, which imparts appropriate flexibility to the film and further improves the formability when the film is attached to a molded article and the shape retention during and after attachment to the molded article.

[0086] The advantages of having the molecular weight between crosslinks within the above range will be explained below. The degree of crosslinking formed between the (A) (meth)acrylic resin or (B) polyol compound and the (C) isocyanate compound in the thermosetting resin composition affects the physical properties of the film. As mentioned above, when the crosslinking is dense, the film becomes hard and difficult to stretch, which reduces formability when attached to an article, but improves chemical resistance. Conversely, when the crosslinking is sparse, the film becomes easy to stretch, improving formability but reducing chemical resistance, creating a trade-off. In the present embodiment, it is believed that the degree of crosslinking of the entire thermosetting resin composition is set to a somewhat sparse state, and while maintaining the formability of the film, the glass transition temperature of the film is increased by introducing a heteropolycyclic skeleton, thereby compensating for the decrease in chemical resistance due to the sparse crosslinking, and achieving both formability and chemical resistance.

[0087] The molecular weight between crosslinks of the film is measured and calculated as follows. Using the same test piece as used for measuring the glass transition temperature described above, the storage modulus (E') is measured at a frequency of 1.0 Hz and at temperatures ranging from -40 to 160°C. The minimum value E' of the storage modulus (E') min and E' min The molecular weight between crosslinks is calculated using the following formula from the absolute temperature T, gas constant R, and film density ρ. Molecular weight between crosslinks=3ρRT / E' min

[0088] When a film is formed using the thermosetting resin composition of the present embodiment, the lower limit of the breaking elongation of the film at 110°C is preferably 100% or more, more preferably 105% or more, even more preferably 110% or more, and still more preferably 120% or more. The upper limit of the elongation at break of the film at 110° C. is not particularly limited, but is, for example, 350% or less. When the film has a breaking elongation at 110°C within the above range, the film has good formability during heat processing. Furthermore, after the film is attached to a molded body while being heated, peeling or breaking of the film can be suppressed during the cooling process, and the film can maintain its shape immediately after attachment (shape retention).

[0089] In this embodiment, the elongation at break at 110° C. is measured as follows. The same test piece as used in the above-mentioned measurement of the glass transition temperature is subjected to tension using a dynamic viscoelasticity measuring device under the conditions of a temperature of 110°C, a chuck distance of 5 mm, a tension speed of 0.083 mm / s, and a tension mode, and the elongation (%) of the test piece at the time of break is defined as the breaking elongation (%).

[0090] <Films and articles equipped with films> The film of this embodiment can be obtained, for example, by applying a thermosetting resin composition in which the above components are dissolved or dispersed in a solvent to a release film or adhesive sheet. The coating method is not particularly limited, and examples thereof include airless spraying, air spraying, electrostatic coating, roll coating, flow coating, spin coating, and dipping. After coating, the coating is cured, for example, at 20 to 160°C for 10 minutes to 10 days, preferably at 60 to 120°C for 20 minutes to 7 days, and then allowed to cool to room temperature to obtain the final film. The curing temperature and time may be adjusted appropriately taking into account the heat resistance of the release film and adhesive sheet.

[0091] The film of the present embodiment may also be a film having a functional layer laminated on at least one surface of the film. The structure of the film will be explained with reference to the drawings. 1 to 3 are diagrams schematically illustrating an example of a film and a shaped product (molded product) according to the present embodiment. 1 shows that a film 1 and a functional layer 2 are provided in this order on a shaped object 4. In other words, the functional layer 2 is the outermost layer of the article. 2 shows that the functional layer 3 and the film 1 are provided in this order on the shaped object 4. That is, the functional layer 3 is a layer sandwiched between the shaped object 4 and the film 1. FIG. 3 shows that on a shape 4 a first functional layer 3, a film 1 and a second functional layer 2 are provided in this order.

[0092] In these figures, examples of functional layers that are the outermost layers of the article include an anti-reflection layer, an anti-fouling layer, an anti-fogging layer, an anti-static layer, an antibacterial / anti-viral layer, and a decorative layer. In these figures, examples of functional layers sandwiched between the shaped object and the film include an adhesive layer and a decorative layer.

[0093] The film of the present embodiment may also be a film on which no functional layer is laminated.

[0094] The film of the present embodiment may contain a functional component, thereby imparting functionality to the film itself. The functional component is not particularly limited, and known components contained in films that are used by being attached to the surface of an article can be applied.

[0095] Furthermore, in this embodiment, after forming the film of this embodiment on a synthetic resin film, the film formed in film form may be transferred to an article by an appropriate transfer process, and then the synthetic resin film may be peeled off to obtain an article having the film.

[0096] The film of the present embodiment may be a laminated film including the above-described film and a base layer such as a synthetic resin film. Such a laminated film can be attached to an article together with the synthetic resin film. The base layer is different from the functional layer described above. The laminated structure film can be obtained by applying the above-mentioned thermosetting resin composition (containing a solvent) to the surface of a suitable substrate layer, drying the solvent, and thermally curing the composition.

[0097] The material of the substrate layer is not particularly limited and can be appropriately selected from the viewpoints of processability (ease of stretching), durability, etc. Preferably, it is at least one selected from the group consisting of polyester, polyurethane, polyvinyl chloride, triacetyl cellulose, polyacrylic resin, polycarbonate, and thermoplastic polyimide. In particular, thermoplastic polyurethane is preferred from the viewpoint of processability (ease of stretching). The substrate layer is typically substantially transparent, but may be colored from the viewpoint of design or the like.

[0098] The thickness of the base layer is preferably 30 to 250 μm, more preferably 50 to 200 μm. By appropriately adjusting the thickness, it is believed that the formability and shape retention when attached to a molded article can be further improved.

[0099] The article (molded article) to which the film of the present embodiment is attached is not particularly limited, but examples thereof include the following articles. Electrical and electronic devices such as mobile phones, smartphones, PCs, PC peripherals (keyboards, printers, external disks, etc.), watches, audio equipment, and various office automation equipment. · Home appliances such as refrigerators, vacuum cleaners, microwave ovens, etc. ·Woodworking products such as stairs, floors, desks, chairs, dressers and other furniture. ·Vehicles such as automobiles and motorcycles or their parts: More specifically, vehicle bodies, interior parts (meter panels, dashboards, handlebars, etc.), bumpers, spoilers, door handles, headlights, taillights, aluminum wheels, motorcycle gas tanks, etc. Before coating, the above-mentioned article may be subjected to degreasing, surface treatment, etc. Furthermore, a primer coat may be applied to improve adhesion, etc.

[0100] The final thickness of the film is preferably 10 to 200 μm, and more preferably 30 to 150 μm. By appropriately adjusting the film thickness, it is expected that a good appearance and flexibility and elasticity as a film can be achieved at the same time.

[0101] <How to apply the film to an item> The film of this embodiment can be attached to an article (shaped object) by any known method, specifically, an out-molding method, an in-molding method, or the like.

[0102] The out-molding method is a method in which a film is attached to a molded object using a vacuum / compressed air molding machine, etc. Hereinafter, a specific description will be given with reference to the drawings. A vacuum / compressed air molding machine is typically a device as shown in I. of Figure 4, which is equipped with a pair of boxes (upper box 10A and lower box 10B) whose internal pressure can be adjusted to any desired level when sealed, a heating means (heater 30) that can heat the inside of the boxes to a high temperature, and a movable base (base 90). Using this device, for example, a film can be attached to an article (shaped object) in the following procedure. (1) As shown in I of Fig. 4, the article (shaped object) 70 is placed on the base 90, and the film 110 is placed in the opening at the top of the lower box 10B. In I of Fig. 4, the article (shaped object) 70 is placed on the base 90 via the mold 50 to prevent it from wobbling or moving. (2) The upper box 10A and the lower box 10B are fitted together to seal the inside of the device. Then, the film 110 is heated and softened using the heater 30. The pressure inside the lower box 10B, in which the article (shaped object) 70 is set, is reduced (II. in FIG. 4). (3) The base 90 is pushed up from below, bringing the article (shaped object) 70 into contact with the softened film 110. At this time, it is preferable to create high pressure inside the upper box 10A while pushing up from below. This makes it easier for the film 110 to adhere sufficiently to the substrate due to the pressure difference between the side of the film 110 and the side of the article (shaped object) 70, in addition to the force from the pushing up (III in FIG. 4). (4) After cooling, the article (shaped object) 70 with the attached film 110 is taken out. If necessary, excess film 110 is trimmed (IV in FIG. 4).

[0103] Unlike the out-molding method, in the in-molding method, the film is applied at the same time as the article (shaped object) is formed. In the in-mold method, a film is placed in an injection mold beforehand, and the resin or other material that will become the material for the article is then injected into the mold, thereby simultaneously forming the article and attaching the film to it.

[0104] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. Below, examples of reference forms are given. 1. (A) a (meth)acrylic resin containing a hydroxy group; (B) a polyol compound different from the component (A); (C) a polyisocyanate compound, A thermosetting resin composition, wherein at least one of the components (A), (B) and (C) has a heteropolycyclic skeleton. 2. The component (A) has the heteropolycyclic skeleton. 1. The thermosetting resin composition according to claim 1. 3. The content of the component (A) is 10% by mass or more and 70% by mass or less, based on 100% by mass of the total solid content of the thermosetting resin composition. 2. The thermosetting resin composition according to claim 1. 4. The component (B) has the heteropolycyclic skeleton. The thermosetting resin composition according to any one of 1. to 3. 5. The content of the component (B) is 5% by mass or more and 60% by mass or less, based on 100% by mass of the total solid content of the thermosetting resin composition. 4. The thermosetting resin composition according to claim 4. 6. The component (C) has the heteropolycyclic skeleton. 1. The thermosetting resin composition according to any one of 1. to 5. 7. The content of the component (C) is 5% by mass or more and 60% by mass or less, based on 100% by mass of the total solid content of the thermosetting resin composition. 6. The thermosetting resin composition according to claim 6. 8. The heteropolycyclic skeleton is an isosorbide-derived skeleton. The thermosetting resin composition according to any one of 1. to 7. 9. In addition to the component (B) containing the heteropolycyclic skeleton, a polyol compound having a molecular weight of 5,000 or less is contained. 4. The thermosetting resin composition according to 4. or 5. 10. The glass transition temperature (°C) of the film formed under the conditions described below in [Film formation conditions] is 35°C or higher and 140°C or lower, as measured under the conditions described below in [Glass transition temperature measurement conditions]. 10. The thermosetting resin composition according to any one of 1. to 9. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator at a coating thickness of 10 mils and allowed to stand for one minute. After allowing to stand, the coated substrate was cured at 80°C for five days. It was then allowed to stand for one week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Glass transition temperature measurement conditions] The film formed under the above [Film Forming Conditions] was cut into test pieces of 5 mm wide and 50 mm long. The test pieces were used to measure dynamic viscoelasticity at a frequency of 1.0 Hz and a temperature range of -40 to 160°C, and the maximum loss tangent (tanδ) was measured. max is the glass transition temperature (°C). 11. The inter-crosslink molecular weight of a film formed under the conditions described below in [Film formation conditions] is 500 or more and 15,000 or less, as measured under the conditions described below in [Inter-crosslink molecular weight measurement conditions]. The thermosetting resin composition according to any one of 1. to 10. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator at a coating thickness of 10 mils and allowed to stand for one minute. After allowing to stand, the coated substrate was cured at 80°C for five days. It was then allowed to stand for one week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Crosslink molecular weight measurement conditions] The film formed under the above [Film Forming Conditions] was cut into test pieces of 5 mm wide and 50 mm long. The minimum value E' of the storage modulus (E') measured at a frequency of 1.0 Hz and a temperature range of -40 to 160°C using the test pieces was min and E' min The molecular weight between crosslinks is calculated using the following formula from the absolute temperature T, gas constant R, and film density ρ. Molecular weight between crosslinks=3ρRT / E' min 12. The breaking elongation of the film formed under the conditions described below in [Film formation conditions] is 100% or more, as measured under the conditions described below in [Breaking elongation measurement conditions]. 12. The thermosetting resin composition according to any one of 1. to 11. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator at a coating thickness of 10 mils and allowed to stand for one minute. After allowing to stand, the coated substrate was cured at 80°C for five days. It was then allowed to stand for one week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Breaking elongation measurement conditions] The film formed under the [Film Forming Conditions] was cut into test pieces measuring 5 mm in width and 50 mm in length. The test pieces were tensioned using a dynamic viscoelasticity measuring device at a temperature of 110°C, a chuck distance of 5 mm, a tension speed of 0.083 mm / s, and in tension mode. The elongation (%) of the test piece at the time of break was taken as the breaking elongation (%). 13. When the heteropolycyclic skeleton is an isosorbide-derived skeleton, the content ratio of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition, calculated by the method described below in [Content ratio (% by mass) of structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition], is 3% by mass or more and 25% by mass or less, relative to 100% by mass of the total solid content of the thermosetting resin composition; 13. The thermosetting resin composition according to any one of 1. to 12. [Content (mass%) of structural units containing heteropolycyclic skeletons in thermosetting resin composition] The content ratio of the molecular weight corresponding to the portion obtained by removing hydrogen atoms from two hydroxy groups bonded to a five-membered ring of the isosorbide represented by the above formula (1) in the thermosetting resin composition is defined as the content ratio (mass%) of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition. 14. A film formed from a cured product of the thermosetting resin composition according to any one of 1. to 13. 15. 14. A film having a functional layer laminated on at least one surface of the film described in 14. 16. 14. or 15. A laminated film comprising the film according to claim 14 or 15. and a substrate layer, The laminated structure film, wherein the material of the substrate layer is at least one selected from the group consisting of polyester, polyurethane, polyvinyl chloride, triacetyl cellulose, polyacrylic resin, polycarbonate, and thermoplastic polyimide. 17. An article comprising the film according to 14. or 15. or the laminated structure film according to 16. [Example]

[0105] The embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these examples.

[0106] <(A) (Meth)acrylic resin> (A) (meth)acrylic resin was synthesized according to Synthesis Examples 1 to 4 below.

[0107] The materials used in the synthesis of (A) (meth)acrylic resin are as follows. For materials without a manufacturer's name, commercially available products were used as appropriate. ·MAA: methacrylic acid MMA: Methyl methacrylate BA: n-butyl acrylate HEMA: 2-hydroxyethyl methacrylate CHMA: Cyclohexyl methacrylate IB-XA: Isobornyl acrylate Plaxel FA5: Polycaprolactone-modified hydroxyethyl acrylate (5-mol caprolactone adduct, molecular weight 689, hydroxyl value 74-84 mgKOH / g), manufactured by Daicel Corporation Plaxel FA2D: Daicel Corporation, polycaprolactone-modified hydroxyethyl acrylate (2-mol caprolactone adduct, molecular weight 344, hydroxyl value 157-167 mgKOH / g) Karenz MOI: 2-methacryloyloxyethyl isocyanate, manufactured by Showa Denko K.K. Isosorbide: POLYSORB PA: Isosorbide manufactured by ROQUETTE (molecular weight 146, hydroxyl value 768 mg KOH / g, solid content 100% by mass) 2,2'-Azobis(2-methylbutyronitrile) (ABN-E): Manufactured by Japan Finechem Co., Ltd., product name: ABN-E

[0108] <Synthesis Example 1> Synthesis of (meth)acrylic resin (A) containing hydroxy groups A flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube was charged with 90 parts by mass of methyl ethyl ketone, and the temperature was raised to 80°C with stirring. In a separate container, a mixed solution (monomer solution) was prepared by adding 64 parts by mass of methyl methacrylate (MMA), 10 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 25 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA-5), 1 part by mass of methacrylic acid (MAA), 10 parts by mass of methyl ethyl ketone, and 2 parts by mass of 2,2-azobis(2-methylbutyronitrile) (ABN-E). This monomer solution was added dropwise to the flask over 2 hours and reacted at 80°C for 6 hours with stirring to obtain a resin solution (solid content 50% by mass) containing (A) (meth)acrylic resin. The weight average molecular weight (Mw) of the obtained (A) (meth)acrylic resin was 19,000.

[0109] <Synthesis Example 2> Synthesis of (meth)acrylic resin (A) containing hydroxy groups In the same manner as in Synthesis Example 1, a (meth)acrylic resin (A) was obtained at the blending ratios shown in Table 1 (values ​​are parts by mass).

[0110] Synthesis Example 3: Synthesis of (meth)acrylic resin (A) containing hydroxy groups In the same manner as in Synthesis Example 1, a (meth)acrylic resin (A) was obtained at the blending ratios shown in Table 1 (values ​​are parts by mass).

[0111] <Synthesis Example 4> Synthesis of (meth)acrylic resin (A) containing a heteropolycyclic skeleton and a hydroxy group 50 parts by mass of isosorbide and 50 parts by mass of methyl ethyl ketone were placed in a flask equipped with a stirrer, a thermometer, and a condenser, and the temperature was raised to 80°C with stirring. In a separate container, a mixed solution was prepared by adding 50 parts by mass of 2-methacryloyloxyethyl isocyanate (Karends MOI), 0.06 parts by mass of a urethane catalyst (dibutyltin dilaurate), 0.2 parts by mass of a polymerization inhibitor (hydroquinone monomethyl ether (MEHQ)), and 50 parts by mass of methyl ethyl ketone. This mixed solution was added dropwise to the flask over 2 hours, and the reaction was carried out at 80°C for 6 hours with stirring, theoretically obtaining a product in which one of the two hydroxyl groups of isosorbide had reacted with an isocyanate compound (hereinafter referred to as Monomer A). Next, 56 parts by mass of methyl ethyl ketone was placed in a flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, and the temperature was raised to 80°C with stirring. In a separate vessel, a mixed solution (monomer solution) was prepared by adding 65 parts by mass of MMA, 68 parts by mass of Monomer A, 1 part by mass of MAA, 10 parts by mass of methyl ethyl ketone, and 2 parts by mass of ABN-E. This monomer solution was added dropwise to the flask over 2 hours, and the mixture was allowed to polymerize at 80°C for 6 hours while stirring, to obtain a resin solution (solid content 50% by mass) containing (A) (meth)acrylic resin having a heteropolycyclic skeleton and a hydroxy group.

[0112] The hydroxyl value, weight average molecular weight (Mw) and glass transition temperature of each of the (meth)acrylic resins (A) obtained in Synthesis Examples 1 to 4 were determined by the following methods, and the results are shown in Table 1 below.

[0113] <Hydroxyl value> Measurements were made and calculated in accordance with the method specified in "7.1 Neutralization titration method" of JIS K 0070 "Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products." The acid value is also required to calculate the hydroxyl value. The acid value was also measured and calculated according to the method specified in "3.1 Neutralization titration method" of the JIS standard.

[0114] <Weight average molecular weight> Measurements and calculations were carried out by gel permeation chromatography (GPC) using the following equipment and conditions. Equipment used: HLC8220GPC (manufactured by Tosoh Corporation) Columns used: TSKgel SuperHZM-M, TSKgel GMHXL-H, TSKgel G2500HXL, TSKgel G5000HXL (manufactured by Tosoh Corporation) Column temperature: 40℃ Standard material: TSKgel standard polystyrene A1000, A2500, A5000, F1, F2, F4, F10 (manufactured by Tosoh Corporation) Detector: RI (differential refractive index) detector Eluent: tetrahydrofuran Flow rate: 1ml / min

[0115] <Glass transition temperature of (meth)acrylic resin (A)> The glass transition temperature of the (meth)acrylic resin (A) was calculated based on the compounding ratio of the monomers used, using the Fox formula below. 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+(W3 / Tg3)+···+(W n / Tg n ) [Wherein, Tg is the desired glass transition temperature (K) of the (meth)acrylic resin (A), W1, W2, W3...W n are the mass fractions of the respective monomers, Tg1, Tg2, Tg3, Tg n indicates the glass transition temperature (K) of a homopolymer composed of monomers corresponding to the mass fraction of each monomer.] It should be noted that the glass transition temperature of isosorbide listed in Table 1 is unknown and therefore not taken into consideration, and the glass transition temperature was determined using only monomers whose glass transition temperatures are known.

[0116] [Table 1]

[0117] [(B) Polyol compound] (B) As the polyol compound, the following was used. ((B) Polyol Compound Having a Heteropolycyclic Skeleton) Isosorbide: POLYSORB PA: Isosorbide manufactured by ROQUETTE (molecular weight 146, hydroxyl value 768 mg KOH / g, solid content 100% by mass) BENEBiOL HS0840B: Mitsubishi Chemical Corporation, isosorbide-based polycarbonate diol (molecular weight 800, hydroxyl value 140 mg KOH / g, solid content 100% by mass) ((B) Polyol Compound Not Having a Heteropolycyclic Skeleton) Plaxel 220N: Polycaprolactone diol (molecular weight 2000, hydroxyl value 53 to 59 mg KOH / g, solid content 100% by mass) manufactured by Daicel Corporation Plaxel 410D: manufactured by Daicel Corporation (molecular weight 1000, hydroxyl value 224 mg KOH / g, solid content 100% by mass)

[0118] [(C) Polyisocyanate compound] According to Synthesis Example 5 below, a polyisocyanate compound (C) having a heteropolycyclic skeleton was synthesized.

[0119] <Synthesis Example 5> Synthesis of polyisocyanate compound (C) having a heteropolycyclic skeleton A flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube was charged with 25 parts by weight of isosorbide and 25 parts by mass of methyl ethyl ketone, and the temperature was raised to 80°C with stirring. A mixed solution of 75 parts by weight of isophorone diisocyanate and 0.06 parts by mass of a urethane catalyst (dibutyltin dilaurate) was prepared in a separate container. This mixed solution was added dropwise to the flask over 2 hours, and the reaction was carried out at 80°C for 6 hours with stirring. After the reaction was completed, 18 parts by weight of methyl ethyl ketone was added and stirred to obtain a curing agent (solid content 70% by mass) containing a heteropolycyclic skeleton.

[0120] In addition, the following were used as the (C) polyisocyanate compound not having a heteropolycyclic skeleton shown in Table 2. TKA-100: Asahi Kasei Corporation, hexamethylene diisocyanate isocyanurate type (isocyanate group content 23% by mass, solid content 100% by mass), product name Duranate TKA-100 D-127N: Manufactured by Mitsui Chemicals, Inc., bis(isocyanatomethyl)cyclohexane isocyanurate type (isocyanate group content 13.5% by mass, solid content 75% by mass), product name Takenate D-127N Z4470BA: Sumika Covetron Urethane Co., Ltd., isocyanurate type of isophorone diisocyanate (isocyanate group content 11.9% by mass, solid content 70% by mass), product name: Desmodur Z4470BA

[0121] <Examples and Comparative Examples> Various materials were mixed in the ratios shown in Table 2, and appropriate amounts of a leveling agent (BYK-302, polyether-modified polymethylalkylsiloxane solution, manufactured by BYK Japan Co., Ltd.) and a urethane catalyst (dibutyltin dilaurate) were added. The solids concentration was then adjusted by adding a solvent (methyl ethyl ketone). In this way, each thermosetting resin composition (solids content: 50% by mass) was prepared. In Table 2, when each material contains a solvent, the amount is expressed as a solid content (unit: parts by mass).

[0122] Table 2 shows the content (mass %) of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition. The content (% by mass) of the structural unit containing a heteropolycyclic skeleton is calculated as the content ratio of the molecular weight corresponding to the portion obtained by removing hydrogen atoms from two hydroxy groups bonded to the five-membered ring of isosorbide represented by the above formula (1). However, the content when BENEBiOL HS0840B is used is not a value calculated as the content ratio described above, but a reference value calculated based on the bio-content (ASTM D6866 standard) calculated on a carbon basis for BENEBiOL HS0840B.

[0123] <Preparation of test film> Each thermosetting resin composition obtained in the Examples and Comparative Examples was applied to the surface of a polypropylene substrate (manufactured by TP Giken Co., Ltd., 200 mm length × 200 mm width × 2 mm thickness, prepared in accordance with JIS-K6921) using an applicator at a coating thickness of 10 mils and left to stand at room temperature for 1 minute. The coating was then cured at 80°C for 5 days using a warm air dryer. The coating was then left to stand for 1 week in an atmosphere of 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a 60 μm-thick film (hereinafter referred to as test film). The test film thus obtained was subjected to the following physical property tests and evaluations, and the results are shown in Table 2.

[0124] <Glass transition temperature and molecular weight between crosslinks of film> Each test film obtained was cut into test pieces 5 mm wide and 50 mm long. Using these test pieces, dynamic viscoelasticity measurements were performed under the following conditions at 23°C and 50% relative humidity. The maximum loss tangent (tanδ) obtained from this measurement was max was taken as the glass transition temperature (°C) of the film. Apparatus: Dynamic viscoelasticity measuring device RSA-G2 (manufactured by TA Instruments) Measurement mode: Non-resonant forced vibration method (Spring Mode) Heating rate: 5.0℃ / min Chuck distance: 20mm Frequency: 1.0Hz Temperature range: -40 to 160°C In addition, the minimum value E' of the storage modulus (E') obtained by the above measurement min and E' min The molecular weight between crosslinks was calculated from the absolute temperature T, gas constant R, and density ρ of the test film based on the rubber viscoelasticity theory formula shown below. Molecular weight between crosslinks=3ρRT / E' min

[0125] <Elongation at break> Each test film obtained was cut into test pieces 5 mm wide and 50 mm long. Using these test pieces, the elongation at break (%) was measured at 110°C under the following conditions. Apparatus: Dynamic viscoelasticity measuring device RSA-G2 (TA Instruments) Measurement mode: Tensile mode (FRT mode) Pulling speed: 0.083 mm / s Chuck distance: 5mm ·Temperature: 110℃ The measurement of the breaking elongation at 25°C was carried out in the same manner as the measurement of the breaking elongation at 110°C, except that the temperature was set to 25°C.

[0126] <Moldability evaluation> An adhesive sheet (Mold Fit50, manufactured by Nichiei Shinka Co., Ltd.) was attached to each of the obtained test films to form a molding film. To attach this molding film, a molded body (shown in Figure 5) made of ABS (acrylonitrile, butadiene, styrene copolymer synthetic resin) was prepared. This molded body has a three-dimensional curved surface, and in order to attach the molding film to this molded body without any gaps, the molding film must be stretched by a maximum of 100% (i.e., if the molding film can be stretched to more than twice its original area (elongation rate of 100% or more), the film can be attached to the surface of the molded body excluding the bottom surface). Next, the molding film and molded body were placed in a vacuum pressure molding machine (NGF-406T, manufactured by Fuse Vacuum Co., Ltd.) with the adhesive layer of the pressure-sensitive adhesive sheet facing the molded body, and out-mold vacuum pressure molding was performed at 25°C and 110°C, respectively, to attach the molding film to the molded body. After molding, the molded body with the molding film attached was visually observed at 25°C and 110°C, and evaluated according to the following criteria. A score of 3 or higher was considered pass. (Evaluation criteria) 1: Peeling of the molding film was confirmed over the entire surface of the molded body. 2: Wrinkles and whitening were observed in the molding film over a wide area around the edge of the molded body. 3: Some wrinkles and whitening were observed on the molding film at the edge of the molded body. 4: Wrinkles and whitening were observed in a very small area of ​​the molding film at the edge of the molded body. 5: The molding film is applied over the entire surface of the molded body without any defects such as wrinkles or whitening.

[0127] <Evaluation of shape retention (stability)> In the above <Moldability Evaluation>, the molded body that was subjected to out-mold vacuum / pressure molding at 110°C was left to stand for one day in a safe-type oven set at 90°C. The state of the molding film after heating was visually observed and evaluated according to the following criteria as an index of shape retention. A score of 3 or more was considered to be acceptable. (Evaluation criteria) 1: Peeling of the molding film was confirmed over the entire surface of the molded body. 2: Peeling of the molding film was observed over a wide area at the edge of the molded body. 3: Some peeling of the molding film was observed at the edge of the molded body. 4: Peeling of the molding film was observed in a very small area at the edge of the molded product. 5: No particular change is observed over the entire surface of the molded body compared to the state of the molding film before heating.

[0128] <Chemical resistance evaluation> Cured films were prepared in the same manner as in <Preparation of test films>, except that the polypropylene substrate used in preparing each of the obtained test films was changed to an ABS substrate (manufactured by TP Giken Co., Ltd., compliant with JIS K 6873). These were then used as test plates without being peeled off from the ABS substrate. A sunscreen (manufactured by Johnson & Johnson, product name: Neutrogena SPF45) was applied at 0.5 g / 100 cm to the surface (cured film side) of each test plate. 2 The test plate was then spread under the conditions of 1) and heated at 55°C for 4 hours in a hot air dryer. After 4 hours of heating, the test plate was removed from the hot air dryer and the sunscreen was wiped off with a cloth. The surface condition of the cured film was then visually observed and evaluated according to the following criteria. A score of 3 or higher was considered a pass. (Evaluation criteria) 1: In the area where the sunscreen was applied, the cured film had peeled off significantly, exposing the substrate. 2: Peeling of the cured film is observed in some areas where sunscreen was applied. 3: Slight cracking or whitening of the cured film in the area where the sunscreen was applied. 4: Slight whitening is observed in a small area of ​​the cured film in the area where the sunscreen was applied. 5: No particular change was observed on the surface of the cured film compared to before heating.

[0129] [Table 2]

[0130] In Table 2, the thermosetting resin composition containing (A) a (meth)acrylic resin, (B) a polyol compound, and (C) an isocyanate compound, wherein at least one of the components (A), (B), and (C) has a heteropolycyclic skeleton, had good moldability at 110°C and excellent chemical resistance. More specifically, both moldability and chemical resistance at 110°C were achieved in all of the thermosetting resin compositions in which component (A) contained a heteropolycyclic skeleton (Examples 9 and 11), the thermosetting resin compositions in which component (B) contained a heteropolycyclic skeleton (Examples 1 to 6, 8, and 11), and the thermosetting resin compositions in which component (C) contained a heteropolycyclic skeleton (Examples 7 and 10). Incidentally, Example 11 contained heteropolycyclic skeletons in both component (A) and component (B). On the other hand, in the thermosetting resin compositions in which none of the components had a heteropolycyclic skeleton (Comparative Examples 1 and 3) and the thermosetting resin composition not containing component (A) (Comparative Example 2), both moldability and chemical resistance at 110°C were not achieved. In addition, the evaluation results of the elongation at break were also inferior to those of the Examples.

[0131] A more detailed analysis of the Examples reveals that Examples 5 to 10 have higher elongation at break and tend to have better moldability, shape retention (stability), and chemical resistance than the other Examples. These favorable results are likely due to the relatively high glass transition temperature of the film and / or the relatively high molecular weight between crosslinks.

[0132] <Supplementary information> In the above examples, the moldability was evaluated by attaching each test film to a molded body by the out-mold method, and the moldability was good in Examples 1 to 11. Considering these results and the similarities between the out-mold method and the in-mold method, it can be said that the films formed from the thermosetting resin compositions of Examples 1 to 11 can also be suitably applied to the in-mold method. [Explanation of symbols]

[0133] 1 film 2. Functional layer (second functional layer) 3. Functional layer (first functional layer) 4 shaped objects 10A Upper Box 10B Lower Box 30 Heater 50-inch 70 Articles (shaped objects) 90 pedestal 110 Film

Claims

1. (A) a (meth)acrylic resin containing a hydroxy group; (B) a polyol compound different from the component (A); (C) a polyisocyanate compound, A thermosetting resin composition, wherein at least one of the components (A), (B), and (C) has a heteropolycyclic skeleton, the heteropolycyclic skeleton is an isosorbide-derived skeleton, The glass transition temperature of the component (A), calculated using the Fox formula below, is 30 to 100°C, 1 / Tg=(W 1 / Tg 1 )+(W 2 / Tg 2 )+(W 3 / Tg 3 )+...+(W n / Tg n ) [In the formula, Tg is the glass transition temperature (K) of the resin, W 1 , W 2 , W 3 , ... W n are the mass fractions of each monomer, and Tg 1 , Tg 2 , Tg 3 , ... Tg n are the glass transition temperatures (K) of homopolymers composed of monomers corresponding to the mass fractions of each monomer.] For monomers with unknown glass transition temperatures, the glass transition temperature is determined using only monomers with known glass transition temperatures. A thermosetting resin composition, wherein the content of the component (A) is 10 to 70 mass%, the content of the component (B) is 10 to 60 mass%, and the content of the component (C) is 5 to 60 mass%, based on the total solid content of the thermosetting resin composition.

2. The component (A) has the heteropolycyclic skeleton. The thermosetting resin composition according to claim 1 .

3. The component (B) has the heteropolycyclic skeleton. The thermosetting resin composition according to claim 1 or 2.

4. The component (C) has the heteropolycyclic skeleton. The thermosetting resin composition according to any one of claims 1 to 3.

5. containing a polyol compound having a molecular weight of 5,000 or less in addition to the component (B) having a heteropolycyclic skeleton, The thermosetting resin composition according to claim 3.

6. The glass transition temperature (°C) of a film formed under the conditions described below in [Film formation conditions] is 35°C or higher and 140°C or lower, as measured under the conditions described below in [Glass transition temperature measurement conditions]. The thermosetting resin composition according to any one of claims 1 to 5. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator to a coating thickness of 10 mil and allowed to stand for 1 minute. The coated substrate was then cured at 80°C for 5 days. The substrate was then allowed to stand for 1 week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Glass transition temperature measurement conditions] The film formed under the above [Film Forming Conditions] is cut into test pieces of 5 mm width and 50 mm length. The maximum value of the loss tangent tanδ when dynamic viscoelasticity was measured using the test piece at a frequency of 1.0 Hz and a temperature range of -40 to 160°C ｍａｘ is the glass transition temperature (°C).

7. The inter-crosslink molecular weight of a film formed under the conditions described in the following [Film formation conditions], measured under the conditions described in the following [Inter-crosslink molecular weight measurement conditions], is 500 or more and 15,000 or less. The thermosetting resin composition according to any one of claims 1 to 6. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator to a coating thickness of 10 mil and allowed to stand for 1 minute. The coated substrate was then cured at 80°C for 5 days. The substrate was then allowed to stand for 1 week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Crosslink molecular weight measurement conditions] The film formed under the above [Film Forming Conditions] is cut into test pieces of 5 mm width and 50 mm length. The minimum value E' of the storage modulus (E') measured using the test piece at a frequency of 1.0 Hz and a temperature range of -40 to 160°C ｍｉｎ and E' ｍｉｎ The molecular weight between crosslinks is calculated from the absolute temperature T, gas constant R, and film density ρ at the temperature by the following formula. Molecular weight between bridges = 3ρRT / E' ｍｉｎ

8. The breaking elongation of a film formed under the conditions described in the [Film formation conditions] below, measured under the conditions described in the [Breaking elongation measurement conditions] below, is 100% or more. The thermosetting resin composition according to any one of claims 1 to 7. [Film formation conditions] The thermosetting resin composition was applied to a polypropylene substrate using an applicator to a coating thickness of 10 mil and allowed to stand for 1 minute. The coated substrate was then cured at 80°C for 5 days. The substrate was then allowed to stand for 1 week at 25°C and 50% relative humidity, and the cured film was peeled off from the polypropylene substrate to obtain a film with a thickness of 60 μm. [Conditions for measuring elongation at break] The film formed under the above [Film Forming Conditions] was cut into test pieces with a width of 5 mm and a length of 50 mm. The test pieces were tensioned using a dynamic viscoelasticity measuring device under the conditions of a temperature of 110°C, a chuck distance of 5 mm, a tension speed of 0.083 mm / s, and a tension mode, and the elongation (%) of the test piece at the time of break was taken as the breaking elongation (%).

9. the content ratio of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition, calculated by the method described below in [Content ratio (% by mass) of structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition], is 3% by mass or more and 25% by mass or less, relative to 100% by mass of the total solid content of the thermosetting resin composition; The thermosetting resin composition according to any one of claims 1 to 8. [Content (mass%) of structural units containing heteropolycyclic skeletons in thermosetting resin composition] The content ratio of the molecular weight corresponding to the portion obtained by removing hydrogen atoms from two hydroxy groups bonded to a five-membered ring of the isosorbide represented by the following formula (1) in the thermosetting resin composition is defined as the content ratio (mass%) of the structural unit containing a heteropolycyclic skeleton in the thermosetting resin composition. 【Chemical 1】

10. The hydroxyl value of the component (A) is 20 to 150 mgKOH / g. The thermosetting resin composition according to any one of claims 1 to 9.

11. A film formed from a cured product of the thermosetting resin composition according to any one of claims 1 to 10.

12. A film comprising the film according to claim 11 and a functional layer laminated on at least one surface thereof.

13. A laminated film comprising the film according to claim 11 or 12 and a substrate layer, The laminated structure film, wherein the material of the substrate layer is at least one selected from the group consisting of polyester, polyurethane, polyvinyl chloride, triacetyl cellulose, polyacrylic resin, polycarbonate, and thermoplastic polyimide.

14. An article comprising the film according to claim 11 or 12 or the laminated structure film according to claim 13.

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