Primary cured film, secondary cured film, method for producing the same, method for using the same, film laminate, film forming composition, and article

Abstract

The present invention relates to a primary cured film, a secondary cured film, a method for producing the same, a method for using the same, a film laminate, a film forming composition, and an article. The present invention provides a polyisocyanate composition, etc., having at least one isocyanate compound selected from the group consisting of aliphatic isocyanate and alicyclic isocyanate as a skeleton, an average of the total number of isocyanate groups per 1 molecule of polyisocyanate, which are blocked by a blocking agent and which are not blocked by a blocking agent, is 2 or more, and 1% by mole or more and 99% by mole or less of the isocyanate groups in the aforementioned polyisocyanate composition are blocked by a blocking agent to constitute the polyisocyanate composition.

Description

[0001] This application is a divisional application of the application filed on June 25, 2020, with application number 202080047063.6 and invention title "Polyisocyanate composition, film forming composition, film, film laminate, adhesive resin composition and adhesive resin cured product, coating composition and coating cured product". Technical Field

[0002] This invention relates to polyisocyanate compositions, compositions for film forming, films, film laminates, adhesive resin compositions and cured adhesive resins, and compositions and cured coatings for coatings. Background Technology

[0003] Polyisocyanate compositions derived from aliphatic and alicyclic diisocyanates have long been widely used in various applications due to their excellent weather resistance and heat resistance.

[0004] In addition, the end-capped polyisocyanate composition, which is formed by sealing the isocyanate groups of the polyisocyanate composition with an end-capping agent, can maintain the storage stability when mixed with active hydrogen compounds while maintaining the physical properties after curing. Therefore, it is widely used as a curing agent for automotive coatings and the like.

[0005] As an improvement on end-capped polyisocyanate compositions, Patent Document 1 discloses an end-capped polyisocyanate that is sealed with both pyrazole-based and oxime-based end-capping agents to exhibit low-temperature curing properties and adhesion to various substrates. Furthermore, as a technique that balances crosslinking density and curing strain, Patent Document 2 discloses a curable adhesive composition that uses a polyisocyanate composition formed by mixing end-capped and non-end-capped polyisocyanate compounds.

[0006] However, in order to enable various urethane-based thermosetting compositions to exhibit further properties, further improvements to polyisocyanates or terminated polyisocyanates are desired.

[0007] As an example of an area where improvements are desired, decorative films for interior and exterior automotive parts can be cited. As a method for decorating the surface of three-dimensional substrates such as interior and exterior automotive parts, a known method is to attach a designed film (hereinafter referred to as "decorative film") to the surface of the substrate. A representative film attachment method is the vacuum / vacuum forming method. In the vacuum / vacuum forming method, the decorative film is attached to a pre-formed substrate while being stretched at room temperature or in a heated atmosphere using a pressure difference. This method attaches the decorative film to the substrate surface of the part through an operation separate from the substrate forming process, thus enabling the attachment of decorative films to substrates of various materials and shapes using a single vacuum / vacuum forming apparatus. In molded articles obtained from plastics, metals, or other materials, the surface is typically decorated to give it a design or for surface protection.

[0008] As decorative films, laminated films as described in Patent Documents 3 and 4 are known. For decorative films used in vacuum / air-forming methods, high tensile strength is required. Furthermore, when using decorative films on three-dimensional substrates, such as automotive exterior parts, not only tensile strength but also weather resistance and solvent resistance are required. However, the techniques in Patent Documents 3 and 4 have limitations in achieving both tensile strength and solvent resistance simultaneously.

[0009] Furthermore, during the manufacturing, storage, and transportation of the film, it needs to be wound into rolls. At this point, there is a possibility that the wound film pieces may stick together due to adhesion. Therefore, anti-adhesion properties are required to prevent this problem.

[0010] Another example of an area where improvements are desired is optical components. In recent years, optical components have increasingly been used under harsh conditions. In polyester films used for optical components, there is a growing demand for adhesive resin compositions that can exhibit properties such as solvent resistance before lamination, adhesion to various functional layers used as upper layers, and stability under high temperature and humidity. Therefore, there is a desire for polyisocyanate compositions suitable for these applications and adhesive resin compositions using these polyisocyanate compositions.

[0011] Furthermore, in recent years, from the perspective of high functionality, high solvent resistance has become a requirement for curing agents in two-component coating compositions. Patent Document 5 provides a polyisocyanate composition in which the number of isocyanate functional groups is increased to further promote crosslinking of the coating composition. On the other hand, in the case of two-component coating compositions, it is desirable to have a long shelf life when the two components are combined and used as a coating. For the above-mentioned coating compositions, there is a tendency for excellent solvent resistance when the degree of crosslinking of the coating film is increased, but there is a concern that the shelf life of the coating will be shortened when the number of functional groups is increased.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent No. 5371884

[0015] Patent Document 2: Japanese Patent Application Publication No. 2016-027153

[0016] Patent Document 3: Japanese Patent Application Publication No. 2016-203434

[0017] Patent Document 4: Japanese Patent Application Publication No. 2016-120642

[0018] Patent Document 5: Japanese Patent Application Publication No. 2017-82076 Summary of the Invention

[0019] The problem the invention aims to solve

[0020] Using the techniques described in Patent Documents 3 and 4, films with good stretchability can be obtained. However, research has not been conducted on decorative films that combine high stretchability with solvent resistance and adhesion resistance. Furthermore, in the field of optical components, there is a need for polyisocyanate compositions that can exhibit properties such as solvent resistance before lamination when forming adhesive resin cured products, adhesion to various functional layers used as upper layers, and stability under high temperature and humidity conditions. Moreover, from the viewpoint of highly functionalizing two-component coating compositions, it is desirable to have polyisocyanate compositions that can balance higher solvent resistance in the coating film and a longer shelf life for the coating.

[0021] The present invention was made in view of the above circumstances, and provides a polyisocyanate composition, as well as a film forming composition, film, film laminate, adhesive resin composition and adhesive resin cured product, coating composition and coating cured product using the aforementioned polyisocyanate composition. When used as a film forming composition, the polyisocyanate composition maintains good tensile properties of the film and has excellent adhesion resistance and solvent resistance. When used as an adhesive resin composition, it has excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity. When used as a coating composition, it can balance the solvent resistance of the coating film and the shelf life of the coating.

[0022] Solution for solving the problem

[0023] That is, the present invention includes the following methods.

[0024] [1] A polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a backbone.

[0025] The average total number of isocyanate groups blocked by the end-capping agent and the number of isocyanate groups not blocked by the end-capping agent per molecule of polyisocyanate is greater than 2, and

[0026] The aforementioned polyisocyanate composition is formed by blocking more than 1 mol% and less than 99 mol% of the isocyanate groups in the polyisocyanate composition with an end-capping agent.

[0027] [2] According to the polyisocyanate composition of [1], wherein the average of the sum of the isocyanate groups blocked by the end-capping agent and the isocyanate groups not blocked by the end-capping agent per molecule of the aforementioned polyisocyanate is 3 or more.

[0028] [3] The polyisocyanate composition according to [1] or [2], wherein the aforementioned polyisocyanate composition comprises a polyisocyanate represented by the following general formula (I).

[0029]

[0030] (In general formula (I), R) 11 The residue obtained by removing the isocyanate group from the polyisocyanate derived from the aforementioned isocyanate compound. X 11 The structural unit is derived from the aforementioned capping agent. m and n are each independently any integer greater than or equal to 1, and n / (m+n) is greater than or equal to 0.01 and less than or equal to 0.99.

[0031] [4] The polyisocyanate composition according to any one of [1] to [3], wherein 10 mol% and 90 mol% of the isocyanate groups in the aforementioned polyisocyanate composition are blocked by a capping agent to form the polyisocyanate composition.

[0032] [5] A thin film forming composition comprising any one of the polyisocyanate compositions described in [1] to [4].

[0033] [6] The thin film forming composition according to [5] further contains an active hydrogen compound.

[0034] [7] The thin film forming composition according to [6], wherein the aforementioned active hydrogen compound comprises an acrylic polyol.

[0035] [8] The thin film forming composition according to [6], wherein the aforementioned active hydrogen compound comprises a diol.

[0036] [9] A thin film formed by curing the composition for forming a thin film as described in any one of [5] to [8].

[0037]

[10] A thin film laminate comprising at least two layers selected from the group consisting of a substrate layer, a decorative layer and an adhesive layer, wherein at least one of the layers constituting the aforementioned thin film laminate comprises the thin film described in [9].

[0038]

[11] An article comprising the film described in [9] or the film laminate described in

[10] .

[0039]

[12] The article according to

[11] is obtained by a manufacturing method comprising the following steps: a step of attaching the film of [9] or the film laminate of

[10] to the article in a manner following the article while heating, and then a step of curing the attached film or film laminate.

[0040]

[13] An adhesive resin composition comprising any one of the polyisocyanate compositions described in [1] to [4].

[0041]

[14] The adhesive resin composition according to

[13] further contains an active hydrogen compound.

[0042]

[15] An adhesive resin cured product formed by curing the adhesive resin composition described in

[13] or

[14] .

[0043]

[16] A method for manufacturing a laminate, comprising:

[0044] The process of applying the adhesive resin composition described in

[13] or

[14] to at least one adherend; and

[0045] The process of bonding an object coated with the aforementioned adhesive resin composition to another object.

[0046]

[17] The method for manufacturing the laminate according to

[16] further includes a step of heating the aforementioned adhered materials.

[0047]

[18] A coating composition comprising any one of the polyisocyanate compositions described in [1] to [4].

[0048]

[19] The coating composition according to

[18] further contains an active hydrogen compound.

[0049]

[20] A coating curing compound formed by curing the coating composition described in

[18] or

[19] .

[0050]

[21] A composite resin cured product comprising:

[0051] The coating composition described in

[18] or

[19] , and

[0052] The base material can be metal, glass, plastic, or wood.

[0053]

[22] A method for manufacturing a coating film, comprising the step of applying the coating composition described in

[18] or

[19] .

[0054]

[23] A one-time curable film, which is formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a backbone and an active hydrogen-containing composition.

[0055] The primary cured film comprises: at least one functional group X selected from the group consisting of urethane groups, urea groups, and amide groups, generated by curing the aforementioned active hydrogen compound and the aforementioned polyisocyanate composition; an active hydrogen group; and an isocyanate group blocked by a capping agent.

[0056]

[24] According to the primary curing film of

[23] , the ratio γ / β of the number of moles of functional group X contained in the primary curing film to the number of moles of isocyanate groups blocked by the end-capping agent is 0.1 or more and 9.0 or less.

[0057]

[25] The primary curing film according to

[23] or

[24] , wherein the number of moles γ of functional group X contained in 1 kg of the aforementioned primary curing film is 0.05 or more and 1.0 or less.

[0058]

[26] A primary cured film according to any one of

[23] to

[25] , wherein the aforementioned active hydrogen-containing compound comprises an acrylic polyol.

[0059]

[27] A primary cured film according to any one of

[23] to

[26] , wherein the aforementioned active hydrogen compound comprises a diol.

[0060]

[28] A secondary curing film, which is formed by further heating and curing the primary curing film described in any one of

[20] to

[27] .

[0061]

[29] A method for manufacturing a secondary curing film, comprising:

[0062] The process of attaching a one-cured film, as described in any one of

[23] to

[27] , to a molded body while heating it at a temperature of 50°C or higher and 140°C or lower;

[0063] The process involves heating the attached resin composition at a temperature above 50°C and below 180°C to cure it.

[0064]

[30] In the manufacturing method of the secondary curing film according to

[29] , the ratio γ / γ′ of the number of moles of functional group X contained in the primary curing film to the number of moles of functional group X contained in the secondary curing film is 0.1 or more and 0.9 or less.

[0065]

[31] In the method for manufacturing a secondary cured film according to

[29] or

[30] , the number of moles γ of functional group X contained in 1 kg of the aforementioned primary cured film is 0.05 or more and 1.0 or less, and

[0066] The number of moles γ' of functional group X contained in 1 kg of the aforementioned secondary cured film is 0.5 or more and 10 or less.

[0067]

[32] A method of using a one-time cured film, comprising:

[0068] The process of attaching a one-cured film, as described in any one of

[23] to

[27] , to a molded body while heating it at a temperature of 50°C or higher and 140°C or lower;

[0069] The process involves heating the attached resin composition at a temperature above 50°C and below 180°C to cure it.

[0070]

[33] A one-time curing film, characterized in that it has a cross-linking structure and a curable functional group A.

[0071]

[34] A composition for forming a thin film, comprising the curable functional group A of the primary curing film described in

[33] , and capable of generating a crosslinked structure of the primary curing film described in

[33] .

[0072]

[35] A secondary curing film, which is formed by curing the primary curing film described in

[33] .

[0073]

[36] A method for manufacturing a secondary curing film, comprising: a step of attaching the primary curing film described in

[33] to a molded body while heating it in a manner that follows the molded body; and a step of curing the attached resin composition thereafter.

[0074]

[37] An article comprising the primary cured film of

[33] or the secondary cured film of

[34] .

[0075]

[38] An article comprising a secondary cured film obtained by the manufacturing method described in

[36] .

[0076] The effects of the invention

[0077] According to the polyisocyanate composition described above, a polyisocyanate composition can be provided that, when used as a film-forming composition, maintains good tensile strength of the film and exhibits excellent resistance to adhesion and solvents; when used as an adhesive resin composition, it exhibits excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity; and when used as a coating composition, it can balance the solvent resistance of the coating film and the shelf life of the coating. The film-forming composition and film according to the above-described method can provide a film that maintains good tensile strength and exhibits excellent resistance to adhesion and solvents. The film laminate according to the above-described method comprises a layer including the aforementioned film and exhibits excellent resistance to adhesion and solvents. The adhesive resin composition and cured adhesive resin according to the above-described method can provide an adhesive resin cured product that exhibits excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity. The coating composition and coating cured product according to the above method can provide a coating cured product with excellent solvent resistance and sufficient shelf life (hereinafter sometimes referred to as "pot life"). Detailed Implementation

[0078] The following provides a detailed description of a method for implementing the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to the following content. The present invention can be suitably implemented through modifications within the scope of its spirit.

[0079] In this specification, "polyisocyanate" refers to a polymer composed of multiple monomers having one or more isocyanate groups (-NCO).

[0080] In addition, in this specification, "polyol" refers to a compound having two or more hydroxyl groups (-OH).

[0081] It should be noted that unless otherwise stated, "(meth)propene*" includes both methpropene* and propylene*.

[0082] Polyisocyanate Compositions

[0083] The polyisocyanate composition of this embodiment has at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a backbone.

[0084] The average value of the total number of isocyanate groups blocked by the end-capping agent and the total number of isocyanate groups not blocked by the end-capping agent in each molecule of polyisocyanate in the polyisocyanate composition (hereinafter sometimes simply referred to as the "total average number of isocyanate groups") is 2 or more. The lower limit of the total average number of isocyanate groups is 2, preferably 2.3, more preferably 3, further preferably 3.4, and particularly preferably 4.5. On the other hand, the upper limit of the total average number of isocyanate groups is not particularly limited, but is preferably 20, more preferably 15, further preferably 10, and particularly preferably 8. That is, the total average number of isocyanate groups is 2 or more, preferably 2 or more and 20 or less, more preferably 2.3 or more and 15 or less, further preferably 3 or more and 10 or less, particularly preferably 3.4 or more and 10 or less, and most preferably 4.5 or more and 8 or less.

[0085] By setting the average total number of isocyanate groups above the aforementioned lower limit, crosslinking properties are further improved, resulting in films with superior resistance to adhesion and solvents. On the other hand, by setting the average total number of isocyanate groups below the aforementioned upper limit, excessive crosslinking can be more effectively suppressed, and the tensile properties of the obtained film can be better maintained.

[0086] The total average number of isocyanate groups is calculated using the following mathematical formula. In the formula, "Mn" is the number-average molecular weight of the polyisocyanate composition measured after heating or dissociation of the end-capping agent. "NCO content" is the percentage of isocyanate groups present relative to the total mass of the polyisocyanate composition, measured after heating or dissociation of the end-capping agent. Furthermore, the NCO content is multiplied by "0.01" to convert the percentage to a decimal. "42" is the formula weight of the isocyanate.

[0087] Average total number of isocyanate groups (average total number of NCO groups) = (Mn × NCO content × 0.01) / 42

[0088] It should be noted that the number-average molecular weight (Mn) can be calculated, for example, by gel permeation chromatography (GPC) of the polyisocyanate composition. The NCO content can be calculated, for example, by titration using a polyisocyanate composition whose end-capping agent has been dissociated by heating or other means. Specifically, the method shown in the examples described later can be used for calculation.

[0089] Alternatively, a polyisocyanate composition can be used as a sample for testing. 13 The total average number of isocyanate groups was determined by C-NMR and calculated.

[0090] Examples of polyisocyanates with an average total number of isocyanate groups within the aforementioned range include isocyanurate-type polyisocyanates formed by trimerizing diisocyanates, biuret-type polyisocyanates formed by reacting 3 isocyanate groups with 1 water molecule, and urea-formate-type polyisocyanates formed by reacting 2 isocyanate groups with 1 alcohol hydroxyl group. From a weather resistance perspective, isocyanurate-type polyisocyanates are preferred as polyisocyanates with an average total number of isocyanate groups within the aforementioned range.

[0091] The proportion of isocyanate groups in the polyisocyanate composition that are blocked by the end-capping agent (hereinafter sometimes referred to as "end-capping rate") is more than 1 mol% and less than 99 mol%.

[0092] When the polyisocyanate composition is used in a film-forming composition, the end-capping rate is preferably 10 mol% or more and 90 mol% or less, more preferably 30 mol% or more and 90 mol% or less, further preferably 50 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.

[0093] By setting the end-capping ratio above the lower limit mentioned above, the tensile properties of the obtained film can be maintained better. On the other hand, by setting the end-capping ratio below the upper limit mentioned above, the processability of the obtained film at room temperature, i.e., its resistance to sticking at room temperature, can be improved.

[0094] On the other hand, when the polyisocyanate composition is used in an adhesive resin composition, the end-capping rate is preferably 10 mol% or more and 90 mol% or less, preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 70 mol% or less, and particularly preferably 40 mol% or more and 60 mol% or less.

[0095] By setting the end-capping ratio to or above the aforementioned lower limit, the resulting cured adhesive resin exhibits superior adhesion to various functional layers used as upper layers (hereinafter sometimes simply referred to as "adhesion to upper layers") and stability under high temperature and high humidity conditions such as 80°C and 95% RH. On the other hand, by setting the end-capping ratio to or below the aforementioned upper limit, the solvent resistance (hereinafter sometimes simply referred to as "solvent resistance before lamination") of the resulting cured adhesive resin before various functional layers are deposited on top of it is improved.

[0096] On the other hand, when using the polyisocyanate composition in a coating composition, the end-capping rate is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and even more preferably 30 mol% or more and 75 mol% or less. By keeping the end-capping rate within the above range, the resulting cured coating exhibits superior solvent resistance and low-temperature drying properties, and also a longer pot life. The end-capping rate can be determined using the method shown in the examples described later.

[0097] The end-capping ratio can be calculated, for example, using titration or the methods shown in the examples described later. Specifically, the end-capping ratio can be determined using the following formula.

[0098] Capping rate = number of moles of capping agent / number of moles of isocyanate groups

[0099] It should be noted that the "molar number of isocyanate groups" in the above formula refers to the number of molar isocyanate groups per unit mass of the polyisocyanate composition after heat treatment to dissociate the capping agent. This can be quantified using the NCO content using the following formula. Here, the NCO content is multiplied by "0.01" to convert the percentage to a decimal. "42" represents the formula weight of the isocyanate.

[0100] Molar number of isocyanate groups = (NCO content × 0.01) / 42

[0101] In addition, the "molar number of capping agent" in the above formula can be quantified by capturing the capping agent during dissociation and measuring it by gas chromatography-mass spectrometry.

[0102] The polyisocyanate composition of this embodiment, by having the above-described structure, is able to provide a polyisocyanate composition that, when used as a film-forming composition, maintains good tensile strength of the film and has excellent adhesion and solvent resistance; when used as an adhesive resin composition, it has excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity; and when used as a coating composition, it can balance the solvent resistance of the coating film and the shelf life of the coating.

[0103] The following describes in detail the components included in the polyisocyanate composition of this embodiment.

[0104] The aforementioned polyisocyanate composition comprises a capped polyisocyanate derived from a polyisocyanate and a capping agent. In a capped polyisocyanate, a portion or all of the isocyanate groups in one molecule of capped polyisocyanate are blocked by a capping agent. Hereinafter, a capped polyisocyanate in which a portion of the isocyanate groups in one molecule of capped polyisocyanate are blocked by a capping agent is referred to as a "partially capped polyisocyanate." Furthermore, a capped polyisocyanate in which all the isocyanate groups in one molecule of capped polyisocyanate are blocked by a capping agent is referred to as a "fully capped polyisocyanate."

[0105] In addition to capped polyisocyanates, the aforementioned polyisocyanate compositions may also contain uncapped polyisocyanates (hereinafter sometimes referred to as "uncapped polyisocyanates").

[0106] When the polyisocyanate composition contains only capped polyisocyanate, the capping rate can be controlled within the aforementioned range by using partially capped polyisocyanate alone or by combining it with partially capped and fully capped polyisocyanate by adjusting the mixing ratio. On the other hand, when the polyisocyanate composition contains both capped and uncapped polyisocyanate, the capping rate can be controlled within the aforementioned range by adjusting the mixing ratio of partially or fully capped polyisocyanate with uncapped polyisocyanate.

[0107] [Polyisocyanates]

[0108] The polyisocyanate used as a raw material in the polyisocyanate composition is derived from at least one isocyanate compound selected from the group consisting of aliphatic and alicyclic isocyanates, and has the skeleton of that isocyanate compound. The polyisocyanate may contain isocyanurate, biuret, urethane, oxadiazinetrione, urea, or carbamate groups, and preferably contains an isocyanurate group. The isocyanate compound that forms the skeleton of the polyisocyanate is not particularly limited, but specifically, it is preferred to have a structure that does not contain aromatic rings such as benzene rings.

[0109] (Aliphatic isocyanates)

[0110] As for aliphatic isocyanates, there are no particular limitations. Specifically, examples include aliphatic monoisocyanates, aliphatic diisocyanates, lysine triisocyanates, and 4-isocyanate methyl-1,8-octamethylene diisocyanate (trimeric triisocyanate), etc. Among them, aliphatic diisocyanates are preferred.

[0111] There are no particular limitations on the aliphatic diisocyanate used. Specifically, aliphatic diisocyanates with 4 or more carbon atoms and 30 or fewer are preferred. Examples include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as "HDI"), 2,2,4-trimethyl-1,6-diisocyanate hexane, and lysine diisocyanate. Among these, HDI is preferred from the perspective of industrial availability. A single aliphatic diisocyanate may be used, or two or more may be used in combination.

[0112] (Alicyclic isocyanates)

[0113] As an alicyclic isocyanate, there is no particular limitation; specifically, examples include alicyclic monoisocyanates and alicyclic diisocyanates. Among them, alicyclic diisocyanates are preferred.

[0114] There are no particular limitations on the alicyclic diisocyanate, but alicyclic diisocyanates with 8 or more but less than 30 carbon atoms are preferred. Examples include isophorone diisocyanate (hereinafter referred to as "IPDI"), 1,3-bis(isocyanate methyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated phenylenediamine diisocyanate. Among these, IPDI is preferred from the viewpoints of weather resistance and industrial availability. A single alicyclic diisocyanate may be used, or two or more may be used in combination.

[0115] [End-capping agent]

[0116] There are no particular limitations on end-capping agents; specifically, compounds having one active hydrogen atom in the molecule can be listed. Examples of such end-capping agents include alcohols, alkylphenols, phenols, active methylene compounds, thiols, acid amides, acid imides, imidazoles, ureas, oximes, amines, imines, pyrazoles, and triazoles. These end-capping agents can be used alone or in combination of two or more. More specific examples of end-capping agents are shown below.

[0117] As an alcohol compound, there is no particular limitation. Specifically, examples include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.

[0118] As alkylphenol compounds, there are no particular limitations. Specifically, examples include monoalkylphenols and dialkylphenols that have alkyl groups with 3 or more but fewer than 12 carbon atoms as substituents. Examples of monoalkylphenols include n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, and n-nonylphenol. Examples of dialkylphenols include di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol.

[0119] As phenolic compounds, there are no particular limitations. Specifically, examples include phenol, cresol, ethylphenol, styrenated phenol, and hydroxybenzoic acid esters.

[0120] As an active methylene compound, there is no particular limitation. Specifically, examples include dimethyl malonate, diethyl malonate, diisopropyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, ethyl isobutyrylate, etc.

[0121] As a thiol compound, there is no particular limitation; specifically, examples include butyl thiol and dodecyl thiol.

[0122] As an acid amide compound, there are no particular limitations. Specifically, examples include acetanilide, acetamide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam.

[0123] As an acid imide compound, there is no particular limitation; specifically, examples include succinic imide and maleic imide.

[0124] As imidazole compounds, there are no particular limitations; specifically, examples include imidazole, 2-methylimidazole, etc.

[0125] As urea compounds, there are no particular limitations; specifically, examples include urea, thiourea, and ethylene urea.

[0126] As oxime compounds, there are no particular limitations. Specifically, examples include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc.

[0127] As an amine compound, there are no particular limitations. Specifically, examples include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine.

[0128] As an imine compound, there is no particular limitation; specifically, examples include ethyleneimine and polyethyleneimine.

[0129] As a pyrazole compound, there is no particular limitation. Specifically, examples include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc.

[0130] As a triazole compound, there is no particular limitation; specifically, examples include 1,2,4-triazole, 1,2,3-triazole, etc.

[0131] From the perspective of ease of acquisition and the viscosity, curing temperature, and curing time of the resulting polyisocyanate composition, acid amide compounds, oxime compounds, active methylene compounds, or pyrazole compounds are preferred. Furthermore, considering the ease of synthesis when some isocyanate groups remain in the polyisocyanate composition, acid amide compounds, oxime compounds, or pyrazole compounds are more preferred. Specifically, methyl ethyl ketone oxime, ε-caprolactam, diethyl malonate, 3-methylpyrazole, or 3,5-dimethylpyrazole are preferred, further preferred, particularly preferred, and most preferably 3,5-dimethylpyrazole.

[0132] [Partially capped polyisocyanates]

[0133] The polyisocyanate composition preferably comprises a partially capped polyisocyanate represented by the following general formula (I) (hereinafter sometimes referred to as "partially capped polyisocyanate (I)").

[0134]

[0135] (In general formula (I), R) 11 The residue obtained by removing the isocyanate group from the polyisocyanate derived from the aforementioned isocyanate compound. X 11 The structural unit is derived from the aforementioned capping agent. m and n are each independently any integer greater than or equal to 1, and n / (m+n) is greater than or equal to 0.01 and less than or equal to 0.99.

[0136] Partially capped polyisocyanates (I) are derived from polyisocyanates and capping agents. A portion of the isocyanate group in a molecule of capped polyisocyanate is blocked by the capping agent.

[0137] As shown in general formula (I), X is a structural unit derived from the capping agent. 11 The amide bond formed by the reaction of the active hydrogen of the capping agent with the isocyanate group, and the residue R obtained by removing the isocyanate group from the isocyanate compound. 11 Combine.

[0138] (R 11 )

[0139] R 11It is a residue obtained by removing the isocyanate group from the polyisocyanate derived from the above isocyanate compound. That is, R 11 The selection is made by choosing at least one alkyl group from the group consisting of aliphatic alkyl groups and alicyclic alkyl groups that contain a specific functional group. Examples of specific functional groups include isocyanurate group, biuret group, urethane group, oxadiazinetrione group, urea group, carbamate group, etc. 11 The alkyl group may contain only one of these functional groups, or it may contain two or more of them.

[0140] (X 11 )

[0141] X 11 These are structural units derived from the capping agent, or more precisely, residues obtained by removing active hydrogen from the capping agent. As X 11 Structural units from the same end-capping agents exemplified in the above-mentioned "end-capping agents" can be listed. Among them, X... 11 Preferably, the structural units are derived from acid amide compounds, oxime compounds, active methylene compounds, or pyrazole compounds. More preferably, structural units are derived from acid amide compounds, oxime compounds, or pyrazole compounds. Specifically, structural units derived from methyl ethyl ketone oxime, ε-caprolactam, diethyl malonate, 3-methylpyrazole, or 3,5-dimethylpyrazole are preferred, further preferred, especially preferred, and most preferably preferred.

[0142] (m and n)

[0143] m represents the number of isocyanate groups that are not blocked by the blocking agent in one molecule of partially capped polyisocyanate (I). n represents the number of isocyanate groups that are blocked by the blocking agent in one molecule of partially capped polyisocyanate (I).

[0144] m and n are each an independent integer greater than or equal to 1, and n / (m+n) is greater than or equal to 0.01 and less than or equal to 0.99. From the viewpoint of cross-linking, m is preferably greater than or equal to 2.

[0145] “n / (m+n)” is the ratio of the number of isocyanate groups blocked by the blocking agent to the total number of isocyanate groups not blocked by the blocking agent and the total number of isocyanate groups blocked by the blocking agent in one molecule of partially capped polyisocyanate (I).

[0146] When the polyisocyanate composition is used in a composition for film formation, n / (m+n) is 0.01 or more and 0.99 or less, preferably 0.10 or more and 0.90 or less, more preferably 0.30 or more and 0.90 or less, even more preferably 0.50 or more and 0.90 or less, and particularly preferably 0.50 or more and 0.80 or less.

[0147] Furthermore, when the polyisocyanate composition is used in an adhesive resin composition, n / (m+n) is 0.01 or more and 0.99 or less, preferably 0.10 or more and 0.90 or less, more preferably 0.20 or more and 0.80 or less, even more preferably 0.30 or more and 0.70 or less, and particularly preferably 0.40 or more and 0.60 or less.

[0148] Furthermore, when the polyisocyanate composition is used in a coating composition, n / (m+n) is 0.01 or more and 0.99 or less, preferably 0.10 or more and 0.90 or less, more preferably 0.20 or more and 0.85 or less, and even more preferably 0.30 or more and 0.75 or less.

[0149] Preferred partially-terminated polyisocyanates (I) include, for example, partially-terminated polyisocyanates represented by the following general formula (I-1).

[0150]

[0151] (In general formula (I-1), R) 12 With the above R 11 Same. m1 and n1 are the same as m and n mentioned above, respectively.

[0152] When the polyisocyanate composition of this embodiment is used in a film forming composition, the content of partially capped polyisocyanate can be set to 0 mol% or more and 100 mol% or less relative to the total molar amount of partially capped polyisocyanate, fully capped polyisocyanate and uncapped polyisocyanate, preferably 10 mol% or more and 90 mol% or less, more preferably 30 mol% or more and 90 mol% or less, further preferably 50 mol% or more and 90 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.

[0153] By keeping the content of partially capped polyisocyanates within the above range, the tensile properties of the obtained film can be maintained better.

[0154] Furthermore, when the polyisocyanate composition of this embodiment is used in an adhesive resin composition, the content of partially capped polyisocyanate can be set to 0 mol% or more and 100 mol% or less relative to the total molar amount of partially capped polyisocyanate, fully capped polyisocyanate and uncapped polyisocyanate, preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, further preferably 30 mol% or more and 70 mol% or less, and particularly preferably 40 mol% or more and 60 mol% or less.

[0155] By keeping the content of partially capped polyisocyanates within the above range, it is possible to improve the solvent resistance, adhesion to the upper layer, and stability under high temperature and high humidity before lamination when preparing adhesive resin cured products.

[0156] Furthermore, when using the polyisocyanate composition of this embodiment in a coating composition, the content of partially capped polyisocyanate can be set to 0 mol% or more and 100 mol% or less relative to the total molar amount of partially capped polyisocyanate, fully capped polyisocyanate and uncapped polyisocyanate, preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and even more preferably 30 mol% or more and 75 mol% or less.

[0157] By keeping the content of partially capped polyisocyanates within the above range, the resulting cured coating exhibits superior solvent resistance and low-temperature curing properties, and a longer pot life.

[0158] The content of partially capped polyisocyanates can be determined using the methods shown in the examples described later.

[0159] [Method for manufacturing polyisocyanate compositions]

[0160] Polyisocyanate compositions can be manufactured by reacting polyisocyanates with capping agents.

[0161] Two methods can be cited as examples of methods for manufacturing polyisocyanate compositions.

[0162] (1) A method for producing a polyisocyanate composition containing only partially capped polyisocyanate by reacting a capping agent in a molar amount of 0.01 times to 0.99 times the molar number of isocyanate groups in the polyisocyanate.

[0163] (2) A method for manufacturing a fully capped polyisocyanate, which is formed by completely capping the isocyanate groups of the polyisocyanate with a capping agent, and a polyisocyanate mixed with at least one of an uncapped polyisocyanate and a partially capped polyisocyanate.

[0164] The target polyisocyanate composition can be obtained by using any of the above methods as a method for manufacturing the polyisocyanate composition. From the perspective of the stretchability of the obtained film and the ability to better exhibit solvent resistance before lamination when making adhesive resin cured products, the above method (1) is preferred.

[0165] The reaction of polyisocyanates with capping agents can be carried out using known methods, with or without solvent. When using a solvent, it is necessary to use a solvent that is inert relative to the isocyanate groups. Additionally, a catalyst may be used as needed.

[0166] Examples of solvents include esters, ketones, and aromatic compounds. Examples of esters include ethyl acetate and butyl acetate. Examples of ketones include methyl ethyl ketone. Examples of aromatic compounds include toluene and xylene.

[0167] Examples of catalysts include organometallic salts, tertiary ammonium salts, and alkali metal alkoxides. Examples of metals used in organometallic salts include tin, zinc, and lead. Examples of alkali metals include sodium.

[0168] The lower limit of the reaction temperature between polyisocyanates and end-capping agents such as pyrazole compounds is generally -20°C, preferably 0°C, and more preferably 30°C. On the other hand, the upper limit of the reaction temperature is 150°C, preferably 120°C, and more preferably 100°C.

[0169] That is, the reaction temperature is above -20°C and below 150°C, preferably above 0°C and below 120°C, and more preferably above 30°C and below 100°C.

[0170] By keeping the reaction temperature within the above range, fewer side reactions are generated, and the reaction can proceed at a suitable rate.

[0171] Compositions for Thin Film Formation

[0172] The thin film forming composition of this embodiment contains the following component 1), or component 1) and 2).

[0173] 1) Polyisocyanate compositions described in "Polyisocyanate Compositions";

[0174] 2) Contains active hydrogen compounds

[0175] According to the film forming composition of this embodiment, by containing the above-described polyisocyanate composition, a film with good tensile strength retention and excellent resistance to adhesion and solvents (hereinafter sometimes referred to as "one-time cured film") can be provided.

[0176] <Containing active hydrogen compounds>

[0177] The active hydrogen-containing compound is not particularly limited, but compounds with two or more active hydrogen atoms bonded intramolecularly are preferred. Examples of preferred active hydrogen-containing compounds include polyol compounds, polyamine compounds, alkanolamine compounds, and polythiol compounds. Among these, polyol compounds are preferred from the perspective of obtaining a film that maintains good tensile strength and exhibits excellent weather resistance and solvent resistance.

[0178] [Polyol compounds]

[0179] The polyol compound is not particularly limited, but examples include polyester polyols, acrylic polyols, polyether polyols, polyolefin polyols, fluorinated polyols, polycarbonate polyols, and epoxy resins. Among these, from the perspective of obtaining a film that maintains good tensile strength and has excellent weather resistance and solvent resistance, acrylic polyols, polyester polyols, polyether polyols, or polycarbonate polyols are preferred, and acrylic polyols are more preferred.

[0180] (Polyester polyols)

[0181] As a polyester polyol, it can be obtained, for example, by condensing a single diacid or a mixture of diacids with a single polyol or a mixture of polyols.

[0182] Examples of the aforementioned dicarboxylic acids include succinic acid, adipic acid, dimer acids, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.

[0183] Examples of the aforementioned polyols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerol, pentaerythritol, 2-hydroxymethylpropanediol, and ethoxylated trimethylolpropane.

[0184] Specifically, methods for manufacturing polyester polyols include, for example, mixing the above-mentioned components and then heating them at a temperature of about 160°C to 220°C to carry out a condensation reaction.

[0185] Alternatively, as a method for manufacturing polyester polyols, specifically, a method can be cited as an example of using a polyol to perform ring-opening polymerization of lactones such as ε-caprolactone to obtain polycaprolactone diol or other polycaprolactones, and the obtained polycaprolactones can be used as polyester polyols.

[0186] These polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived from them. In this case, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived from them are particularly preferred from the viewpoints of weather resistance and resistance to yellowing.

[0187] When used as a composition for forming aqueous films, a portion of the remaining dicarboxylic acid or other carboxylic acids can be left in advance, and a water-soluble or water-dispersible resin can be prepared by neutralizing it with a base such as an amine or ammonia.

[0188] (Acrylic polyols)

[0189] As an acrylic polyol, there is no particular limitation. Specifically, examples include, for instance, copolymers of compounds containing olefinic unsaturated monomers with hydroxyl groups, or mixtures thereof, with other compounds containing olefinic unsaturated monomers that can copolymerize with them, or mixtures thereof.

[0190] As a monomer containing an olefinic unsaturated bond and a hydroxyl group, there is no particular limitation. Specifically, examples include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate. Among these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred.

[0191] Other monomers containing olefinic unsaturated bonds that can copolymerize with the aforementioned monomers include, for example, (meth)acrylates, unsaturated carboxylic acids, unsaturated amides, vinyl monomers with hydrolyzable silyl groups, and other polymerizable monomers. One of these may be used alone, or two or more may be used in combination.

[0192] Examples of the aforementioned (meth)acrylates include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, etc.

[0193] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, and itaconic acid.

[0194] Examples of unsaturated amides include acrylamide, N-hydroxymethylacrylamide, and diacetone acrylamide.

[0195] Examples of vinyl monomers with hydrolyzable silyl groups include vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloyloxypropyltrimethoxysilane.

[0196] Other examples of polymerizable monomers include styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0197] For example, acrylic polyols can be obtained by solution polymerization of the above-mentioned monomer components in the presence of known free radical polymerization initiators such as peroxides and azo compounds, and then diluted with organic solvents as needed.

[0198] When an aqueous-based acrylic polyol is obtained, it can be manufactured using known methods such as solution polymerization of an olefinic unsaturated compound to convert it into an aqueous layer, or emulsion polymerization. In this case, water solubility or water dispersibility can be imparted by neutralizing the acidic portions of monomers containing carboxylic acids, such as acrylic acid and methacrylic acid, or monomers containing sulfonic acids, with amines or ammonia.

[0199] (Polyether polyols)

[0200] As for polyether polyols, there are no particular limitations, but specifically they include: polyether polyols obtained by adding epoxide compounds or mixtures thereof to polyhydroxy compounds or mixtures thereof in the presence of a strong alkaline catalyst; polyether polyols obtained by reacting epoxides with polyfunctional compounds such as ethylenediamines; and so-called polymer polyols obtained by polymerizing acrylamides or the like using these polyethers as a medium.

[0201] Examples of the aforementioned polyhydroxy compounds include diglycerides, di(trimethylolpropane), pentaerythritol, dipentaerythritol, sugar alcohols, monosaccharides, disaccharides, trisaccharides, and tetrasaccharides.

[0202] Examples of sugar alcohol compounds include erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

[0203] Examples of monosaccharides include arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and deoxyribose.

[0204] Examples of disaccharides include trehalose, sucrose, maltose, cellulosic disaccharide, gentiobiose, lactose, and melibiose.

[0205] Examples of trisaccharides include metriose, gentiotriose, and pinotriose.

[0206] Examples of tetrasaccharides include stachyose.

[0207] As a strongly basic catalyst, there are no particular limitations. Specifically, examples include hydroxides of alkali metals such as lithium, sodium, and potassium; alkoxides; and alkylamines.

[0208] Examples of the aforementioned epoxides include ethylene oxide, propylene oxide, butane oxide, cyclohexane oxide, and phenylene oxide.

[0209] (Polyolefin polyols)

[0210] As a polyolefin polyol, there are no particular limitations. Specifically, examples include polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene, which have two or more hydroxyl groups.

[0211] (Fluorinated polyols)

[0212] Fluorinated polyols are polyols containing fluorine in their molecules. Examples include copolymers of fluorinated olefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and monocarboxylic acid vinyl esters disclosed in Japanese Patent Application Publication No. 57-34107 (Reference 1) and Japanese Patent Application Publication No. 61-275311 (Reference 2).

[0213] (Polycarbonate polyols)

[0214] The polycarbonate polyol is not particularly limited, but examples include polycarbonate polyols obtained by polycondensation of a low-molecular-weight carbonate compound with the polyol used in the aforementioned polyester polyol. The low-molecular-weight carbonate compound is not particularly limited, but examples include dialkyl carbonates such as dimethyl carbonate; alkylene carbonates such as ethylene carbonate; and diaryl carbonates such as diphenyl carbonate.

[0215] (Epoxy resin)

[0216] As for epoxy resins, there are no particular limitations. Specifically, examples include phenolic varnish-type epoxy resins, glycidyl ether-type epoxy resins, glycol ether-type epoxy resins, epoxy resins of aliphatic unsaturated compounds, epoxy fatty acid esters, polycarboxylic acid ester-type epoxy resins, aminoglycidyl-type epoxy resins, β-methylepichlool-type epoxy resins, cyclic ethylene oxide-type epoxy resins, halogenated epoxy resins, and resorcinol-type epoxy resins.

[0217] (hydroxyl value)

[0218] Regarding the hydroxyl value of the polyol compound, from the perspective of crosslinking density and the mechanical properties of the film, it is preferably 5 mg KOH / g or more and 600 mg KOH / g or less per 1g of polyol compound, more preferably 10 mg KOH / g or more and 500 mg KOH / g or less, and even more preferably 15 mg KOH / g or more and 400 mg KOH / g or less. Furthermore, the acid value of the polyol compound is preferably 0 mg KOH / g or more and 30 mg KOH / g or less. It should be noted that the hydroxyl value and acid value can be determined based on titration.

[0219] [Polyamine compounds]

[0220] The term "polyamine compound" is not particularly limited, but examples include diamines, chain polyamines having three or more amino groups, and cyclic polyamines. Examples of diamines include ethylenediamine, propylenediamine, butanediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine. Examples of chain polyamines having three or more amino groups include dihexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine. Examples of cyclic polyamines include 1,4,7,10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[0221] [Alkanolamine compounds]

[0222] As an alkanolamine compound, there is no particular limitation. Specifically, examples include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono- / di-(n- or iso)propanolamine, ethylene glycol dipropylamine, neopentyl alcoholamine, methylethanolamine, etc.

[0223] [Polythiol compounds]

[0224] As a polythiol compound, there are no particular limitations. Specifically, examples include bis-(2-hydrothioethoxy)methane, dithioethylene glycol, dithioerythritol, and dithiothreitol.

[0225] These active hydrogen compounds can be used alone or in combination of two or more. From the perspective of obtaining films that maintain good tensile strength and exhibit excellent weather resistance and solvent resistance, it is preferable to use acrylic polyols alone or in combination with diols as active hydrogen compounds. The term "diol" here refers to compounds containing two hydroxyl groups among the aforementioned polyol compounds. The term "diol" is not particularly limited; specifically, examples include polyols of the aforementioned "polyester polyols" or compounds containing two hydroxyl groups among the substances exemplified in the polycaprolactone class, and compounds containing two hydroxyl groups among the substances exemplified in the aforementioned "polycarbonate polyols."

[0226] [NCO / OH]

[0227] When the active hydrogen compound is a polyol compound, the molar ratio (NCO / OH) of the isocyanate (-NCO) group to the hydroxyl (-OH) group of the polyisocyanate composition is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and even more preferably 0.5 or more and 2.0 or less. By setting NCO / OH to the lower limit value or above, there is a tendency to obtain a tougher film. By setting NCO / OH to the upper limit value or below, there is a tendency to further improve the smoothness of the obtained film. It should be noted that the molar number of "isocyanate (-NCO) groups in the polyisocyanate composition" used in the calculation of NCO / OH is the total molar number of isocyanate groups not blocked by the end-capping agent and isocyanate groups blocked by the end-capping agent.

[0228] <Other Additives>

[0229] The thin film forming composition of this embodiment may include various additives such as organic solvents, curing promoters, antioxidants, ultraviolet absorbers, light stabilizers, pigments, leveling agents, plasticizers, and surfactants, depending on the purpose and use.

[0230] As an organic solvent, it is preferable to have no functional groups that react with hydroxyl and isocyanate groups, and preferably to be fully compatible with polyisocyanate compositions. There are no particular limitations on such organic solvents; for example, any solvent commonly used as a solvent in coatings is acceptable, including ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylic acid ester compounds, hydrocarbon solvents, etc.

[0231] There are no particular limitations on the type of curing catalyst; specifically, examples include tin-based compounds, zinc compounds, titanium compounds, cobalt compounds, bismuth compounds, zirconium compounds, and amine compounds. Examples of tin-based compounds include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanate, and bis(2-ethylhexanoate)tin. Examples of zinc compounds include zinc 2-ethylhexanoate and zinc naphthenate. Examples of titanium compounds include titanium 2-ethylhexanoate and diisopropoxybis(ethylacetone)titanium. Examples of cobalt compounds include cobalt 2-ethylhexanoate and cobalt naphthenate. Examples of bismuth compounds include bismuth 2-ethylhexanoate and bismuth naphthenate. Examples of zirconium compounds include zirconium tetraacetylacetonate, zirconium oxy2-ethylhexanoate, and zirconium oxy2-naphthenate.

[0232] As antioxidants, there are no particular limitations. Specifically, examples include hindered phenolic compounds, phosphorus compounds, and sulfur compounds.

[0233] As a UV absorber, there are no particular limitations. Specifically, examples include benzotriazole compounds, triazine compounds, and benzophenone compounds.

[0234] As a light stabilizer, there are no particular limitations. Specifically, examples include hindered amine compounds, benzotriazole compounds, triazine compounds, benzophenone compounds, and benzoate compounds.

[0235] As pigments, there are no particular limitations. Specifically, examples include titanium oxide, carbon black, indigo, pearlescent mica, and aluminum.

[0236] As a leveling agent, there are no particular limitations; specifically, silicone oil can be cited as an example.

[0237] As a plasticizer, there are no particular limitations. Specifically, examples include phthalates, phosphoric acid compounds, and polyester compounds.

[0238] As a surfactant, there are no particular limitations. Specifically, examples include well-known anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0239] <Method for manufacturing a composition for thin film formation>

[0240] In the case where the film-forming composition of this embodiment is based on an organic solvent, for example, the above-mentioned polyisocyanate composition is first added as a curing agent to a product obtained by adding other additives such as resins, catalysts, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, and surfactants as needed to a dilution containing an active hydrogen compound or its solvent. Next, an organic solvent is added as needed to adjust the viscosity. Then, by manual stirring or stirring using a stirring machine such as MAZELA, an organic solvent-based film-forming composition can be obtained.

[0241] In the case where the film-forming composition of this embodiment is aqueous, for example, additives such as a curing agent, other resins, catalysts, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, and surfactants that can react with the crosslinking functional groups in the active hydrogen compound are first added to an aqueous dispersion or aqueous solution containing an active hydrogen compound, as needed. Next, the aforementioned polyisocyanate composition or its aqueous dispersion is added as a curing agent, and water and solvent are further added as needed to adjust the viscosity. Then, by forced stirring using a mixer, an aqueous film-forming composition can be obtained.

[0242] Single-cured film F1 and double-cured film F2

[0243] The one-time curing film of this embodiment is formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a backbone and an active hydrogen-containing composition. It includes at least one functional group X selected from the group consisting of urethane groups, urea groups and amide groups generated by curing the aforementioned active hydrogen-containing compound and the aforementioned polyisocyanate composition, an active hydrogen group and an isocyanate group blocked by a capping agent.

[0244] The one-time cured film of this embodiment is formed by curing the above-described film forming composition. The one-time cured film of this embodiment maintains good tensile strength and has excellent resistance to adhesion.

[0245] The one-time cured film of this embodiment is obtained by coating the above-described film-forming composition onto a substrate or the like and curing it at room temperature or by heating. Specifically, the isocyanate groups of the polyisocyanate composition in the film-forming composition react with active hydrogen containing an active hydrogen compound to form a one-time cured film. At this time, by keeping the blocked isocyanate groups in their original state, good stretchability can be exhibited when the one-time cured film is applied. In addition, after applying the one-time cured film to various substrates, it is heated again to dissociate the end-capping agent bound to the isocyanate groups, thereby forming crosslinks. Through this crosslinking formation, the crosslinking density of the film is increased, resulting in a two-time cured film exhibiting weather resistance and solvent resistance.

[0246] As coating methods, known methods such as reverse roller coating, gravure coating, roller coating, die coating, roller brush coating, spray coating, air knife coating, wire bar coating, tube blade coating, dip coating, curtain coating, roller coating, curtain flow coating, spray coating, rotary cup coating, and electrostatic coating can be used.

[0247] The thickness of the one-time cured film is not particularly limited, but is preferably 0.2 μm or more and 500 μm or less, more preferably 1 μm or more and 500 μm or less, even more preferably 5 μm or more and 300 μm or less, and particularly preferably 5 μm or more and 100 μm or less.

[0248] In the fabrication of the primary and secondary cured films in this embodiment, a film-forming composition preferably includes the aforementioned polyisocyanate composition and an active hydrogen-containing composition. By using the aforementioned film-forming composition, a primary cured film containing a crosslinked structure formed by the reaction of isocyanate groups and active hydrogen groups, active hydrogen groups, and isocyanate groups blocked by a capping agent can be obtained. The crosslinked structure contained in the primary cured film can improve the room-temperature processability, i.e., the room-temperature resistance to adhesion, of the resulting film. Furthermore, the active hydrogen groups and isocyanate groups blocked by the capping agent in the primary cured film allow for further crosslinking, resulting in a secondary cured film with excellent solvent resistance.

[0249] The functional group (hereinafter referred to as functional group X) that forms the cross-linked structure through the reaction of isocyanate group and active hydrogen group is not particularly limited, but preferably includes at least one selected from urethane group, urea group and amide group.

[0250] In this embodiment, the ratio γ / β of the number of moles of functional group X (γ) to the number of moles of isocyanate groups blocked by the end-capping agent in 1 kg of the one-time cured film can be set to 0.02 or more and 9.0 or less. γ / β is preferably set to 0.1 or more and 2.4 or less, more preferably 0.1 or more and 1.0 or less, and particularly preferably 0.2 or more and 1.0 or less. By setting γ / β to the lower limit or above, the resulting film exhibits better processability at room temperature, i.e., better resistance to adhesion at room temperature. On the other hand, by setting γ / β to the upper limit or below, the tensile strength of the film can be maintained better.

[0251] Furthermore, in the one-time cured film of this embodiment, the ratio γ / α of the number of moles of functional group X to the number of moles of active hydrogen groups in 1 kg of one-time cured film can be set to 0.1 or more and 9.0 or less. γ / α is preferably set to 0.1 or more and 2.4 or less, more preferably 0.1 or more and 1.0 or less, and particularly preferably 0.2 or more and 1.0 or less.

[0252] In the primary curing film of this embodiment, the ratio β / α of the number of moles of isocyanate groups blocked by the end-capping agent to the number of moles of active hydrogen groups in 1 kg of primary curing film can be set to 0.02 or more and 20 or less. β / α is preferably set to 0.1 or more and 10 or less, more preferably 0.2 or more and 5.0 or less, and particularly preferably 0.5 or more and 2.0 or less.

[0253] Furthermore, the ratio γ / γ' of the number of moles of functional group X contained in 1 kg of primary curing film to the number of moles of functional group X contained in 1 kg of secondary curing film can be set to 0.1 or more and 0.9 or less. γ / γ' is preferably 0.1 or more and 0.7 or less, more preferably 0.1 or more and 0.5 or less, and particularly preferably 0.2 or more and 0.5 or less. By setting γ / γ' to the lower limit or above, the processability of the obtained film at room temperature, i.e., its resistance to adhesion at room temperature, can be improved. On the other hand, by setting γ / γ' to the upper limit or below, the tensile properties of the film can be maintained better.

[0254] The primary curing film in this embodiment is characterized in that the number of moles γ of functional group X contained in 1 kg of primary curing film and the number of moles γ' of functional group X contained in 1 kg of secondary curing film are respectively within the following ranges.

[0255] 1) The molar number γ of functional group X contained in 1 kg of one-time cured film is 0.05 or more and 1.0 or less. γ is preferably 0.05 or more and 0.8 or less, more preferably 0.07 or more and 0.6 or less, and particularly preferably 0.1 or more and 0.4 or less. By setting γ to the lower limit or above, a film with a certain crosslinking density and self-supporting properties can be obtained. On the other hand, by setting γ to the upper limit or below, the tensile properties of the one-time cured film can be maintained.

[0256] 2) The molar number γ' of functional group X contained in 1 kg of the secondary cured film is 0.3 or more and 10 or less. γ' is preferably 0.3 or more and 5.0 or less, more preferably 0.5 or more and 2.0 or less, and particularly preferably 0.5 or more and 1.2 or less. By setting γ' to the lower limit or above, the crosslinking density of the secondary cured film is increased, exhibiting solvent resistance. In addition, by setting γ' to the upper limit or below, the mechanical properties of the secondary cured film can be well maintained.

[0257] In this embodiment, the tensile modulus of the one-time cured film is obtained using a stress-strain curve with the measurement temperature set to the glass transition temperature of the film +10°C and the stretching speed set to 100% / min. For the tensile modulus of the one-time cured film, stress and strain exhibit a linear relationship in the region of 5% to 10% elongation, and when calculated from its slope, it is preferably 0.1 MPa or more and 3.0 MPa or less. By setting the tensile modulus to the upper limit or below, good tensile properties can be obtained; by setting it to the lower limit or above, the required film strength during stretching can be maintained. The tensile modulus is preferably 0.2 MPa or more and 1.5 MPa or less, more preferably 0.3 MPa or more and 1.1 MPa or less, and particularly preferably 0.4 MPa or more and 0.7 MPa or less.

[0258] <Instructions for using the one-time curing film F1>

[0259] As described above, the one-time curing film of this embodiment is used as follows: it is attached to the surface of a pre-formed substrate; or, it is attached to the surface while forming an article using a known molding method. The molded body with the one-time curing film attached is then heated to cure the attached one-time curing film. By going through these processes, a molded body protected by a film with high solvent resistance can be obtained.

[0260] Both methods involve attaching the film to the substrate surface using well-known bonding methods. Specific examples of the former include vacuum forming, air-forming, vacuum / air-forming, and lamination. Specific examples of the latter include in-mold molding and film insert molding.

[0261] It is preferably used in vacuum / air forming, in-mold forming, and film insert forming, especially where high tensile strength is required. More preferably, it is used in vacuum / air forming where films can be attached regardless of the material of the pre-formed substrate.

[0262] There are no particular limitations on the method of applying the one-time curing film. From the viewpoint of the film's conformability to the molded body, it is preferable to apply the one-time curing film to the molded body while heating it at a temperature of 50°C or higher and 140°C in a manner that conforms to the molded body. By setting the heating temperature above the lower limit, the film can be better conformed to the molded body. In addition, by setting the heating temperature below the upper limit, the dissociation of isocyanate groups blocked by the end-capping agent in the one-time curing film can be prevented.

[0263] The heating temperature for further curing the applied primary curing film is preferably set to 50°C or higher and 180°C or lower. The heating temperature is preferably 50°C or higher and 170°C or lower, more preferably 50°C or higher and 160°C or lower, and particularly preferably 100°C or higher and 150°C or lower. By setting the heating temperature within the above range, the isocyanate groups blocked by the capping agent dissociate and react with active hydrogen groups, thereby forming crosslinks and obtaining a film with high solvent resistance.

[0264] Single-cured film F1′ and double-cured film F2′

[0265] The one-time curing film of this embodiment includes a cross-linked structure and a curable functional group A. By having a cross-linked structure, it possesses self-supporting film strength, enabling the film to exhibit processability, i.e., resistance to adhesion. Furthermore, due to the inclusion of functional group A, curing can be performed after film application, ensuring the final film's weather resistance and solvent resistance even if the cross-linking density decreases to a level where good stretchability is maintained during film application.

[0266] In this embodiment, the primary cured film F1′ is obtained as described above by coating a film forming composition onto a substrate or the like and applying an external stimulus to cure it. At this time, by maintaining the film in a state where some of the contained reactive functional groups remain, it exhibits good stretchability during film attachment. Then, by applying an external stimulus to the primary cured film, it is further cured due to the reactive functional groups retained in the primary cured film, thereby obtaining a secondary cured film.

[0267] The crosslinking structure contained in the one-time cured film F1′ is not particularly limited and can be formed by known crosslinking reactions such as condensation polymerization, addition polymerization, and various polymerization reactions. Specifically, examples include: crosslinking based on the polymerization of compounds having carbon unsaturated bonds represented by vinyl and (meth)acryloyl groups; crosslinking based on the ring-opening polymerization of cyclic compounds represented by ethylene oxide; crosslinking by means of amide bonds (polyamide); crosslinking by means of ester bonds (polyester); crosslinking by means of melamine bonds (melamine resin); crosslinking by means of carbonate bonds (polycarbonate); crosslinking by means of urethane bonds (polyurethane); crosslinking by means of urea bonds (polyurea); crosslinking by means of organosilicon bonds (organosilicon resin); crosslinking based on the condensation of phenol and formaldehyde (phenolic resin); crosslinking based on the condensation of urea and formaldehyde (urea resin); crosslinking based on the reaction of epoxy resin with curing agents such as amines, amides, acids, and anhydrides; and crosslinking by means of imino bonds (polyaniline), etc. Crosslinking via urethane bonds, crosslinking via urea bonds, crosslinking via amide bonds, and crosslinking based on (meth)acryloyl groups are preferred, with crosslinking via urethane bonds being particularly preferred.

[0268] Similarly, there is no particular limitation on the curable functional group A contained in the one-time cured film, as long as it contains functional groups required for carrying out known curing reactions. Therefore, functional group A can be a single type, or it can contain multiple functional groups as needed. Specifically, examples of functional groups that can carry out curing reactions as a single type include vinyl, (meth)acryloyl, and silanol groups. Among them, (meth)acryloyl is preferred.

[0269] Furthermore, combinations of functional groups that enable the curing reaction through multiple functional groups can include "active hydrogen groups and isocyanate groups", "carboxyl groups and hydroxyl groups", "epoxy groups and amino, acid, acid anhydride groups", and "amino and formyl (aldehyde) groups". Among these, the combination of "active hydrogen groups and isocyanate groups" is preferred.

[0270] It should be noted that the cross-linking structure contained in the primary cured film and the cross-linking structure formed by functional group A can be the same or different.

[0271] It should be noted that the compound having the curing functional group A can be a compound that does not have a reactive functional group, or it can be a compound that is reactive when the external stimulus described later is applied. These are not particularly limited, and examples include acid anhydrides and terminal isocyanate compounds.

[0272] The cross-linking structure is formed by room temperature or by applying certain external stimuli. Specific types of external stimuli include heating, irradiation with active energy lines, moisture, vibration, electric field, magnetic field, pressure, and pH changes. In the formation of the cross-linking structure contained in the one-time cured film, from the viewpoint of the versatility of the process equipment and productivity, heating, irradiation with active energy lines, and moisture are preferred, heating and irradiation with active energy lines are more preferred, and heating is even more preferred.

[0273] Furthermore, in the formation of the crosslinked structure based on functional group A, from the viewpoint of usage, it is desirable that crosslinking does not occur while the film is being stored. Additionally, from the viewpoint of crosslinking formation after attachment to a structure, heating or irradiation with active energy lines is preferred for efficient formation of the crosslinked structure.

[0274] The secondary curing film is obtained by reacting the curable functional group A contained in the primary curing film.

[0275] Through the reaction of functional group A, the crosslinking density of the film is increased, exhibiting weather resistance and solvent resistance.

[0276] <Compositions for Thin Film Forming>

[0277] The thin film forming composition of this embodiment is characterized by comprising a compound having a crosslinking structure or a compound capable of forming a crosslinking structure, and the aforementioned curable functional group A. By coating this thin film forming composition onto a substrate or the like and applying external stimulation such as heating as needed, a one-time cured thin film comprising the crosslinking structure and curable functional group A is obtained.

[0278] <Instructions for using the one-time curing film F1′>

[0279] The one-time curing film of this embodiment is used as follows: it is attached to the surface of a pre-formed substrate; or, it is attached to the surface while forming an article using a known molding method. The molded body with the one-time curing film attached is then heated to cure the attached one-time curing film. By undergoing this process, an article protected by a film with high solvent resistance can be obtained.

[0280] Regarding the attachment of films, known methods can be used to attach the film to the surface of a substrate. There are no particular limitations on the method; examples include vacuum forming, air-forming, vacuum / air-forming, and lamination of a pre-formed substrate. Furthermore, methods that attach the film during the forming process include in-mold forming and film insert forming.

[0281] It is preferably used in vacuum / air forming, in-mold forming, and film insert forming, especially where high tensile strength is required. More preferably, it is used in vacuum / air forming where films can be attached regardless of the material of the pre-formed substrate.

[0282] Thin Film Laminates

[0283] The film laminate of this embodiment comprises at least two layers selected from the group consisting of a substrate layer, a decorative layer, and an adhesive layer. At least one layer constituting the aforementioned film laminate includes the aforementioned one-cured film F1 or F1'. The film laminate of this embodiment exhibits excellent resistance to adhesion and solvents.

[0284] The film laminate of this embodiment may contain the aforementioned film in either the substrate layer or the decorative layer, or in both layers. Furthermore, the film laminate of this embodiment may contain one (single) layer of the aforementioned film within one of the layers constituting the film laminate, or it may contain two or more layers of the aforementioned film.

[0285] <Decorative Layer>

[0286] As a decorative layer, there are no particular limitations; specifically, examples include coloring layers, pattern layers, etc. The decorative layer can consist of one layer (single layer) or multiple layers (two or more). When the decorative layer consists of multiple layers, the composition, shape, and thickness of the multiple layers can be the same or different from each other, and there are no particular limitations on the combination of these multiple layers as long as it does not impair the effect of the present invention.

[0287] It should be noted that this specification is not limited to the case of decorative layers. "Multi-layers may be the same or different from each other" means that "all layers may be the same, all layers may be different, or only some layers may be the same." In addition, "multi-layers may be different from each other" means that "at least one of the composition, shape, and thickness of each layer is different from each other."

[0288] The thickness of the decorative layer is not particularly limited, but is preferably 0.2 μm or more and 100 μm or less. It should be noted that the "thickness of the decorative layer" referred to here refers to the overall thickness of the decorative layer. For example, the thickness of a decorative layer composed of multiple layers refers to the total thickness of all the layers that make up the decorative layer.

[0289] [Shading layer]

[0290] A coloring layer refers to a layer that displays painted colors, metallic colors, etc. Examples of colorants contained in a coloring layer include: inorganic pigments, organic pigments, aluminum materials, pigments dispersed in binder resins, and printing inks. Examples of inorganic pigments include titanium oxide, carbon black, lead yellow, iron oxide yellow, iron oxide red, and iron oxide red. Examples of organic pigments include phthalocyanine pigments, azo lake pigments, indigo pigments, violet ketone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, and quinacridone pigments. Examples of phthalocyanine pigments include phthalocyanine blue and phthalocyanine green. Examples of quinacridone pigments include quinacridone red. Examples of aluminum materials include aluminum sheets, vapor-deposited aluminum sheets, aluminum sheets coated with metal oxides, and colored aluminum sheets. Examples of pigments dispersed in binder resins include pearlescent materials such as flake mica coated with metal oxides such as titanium oxide and iron oxide, and synthetic mica. Examples of binder resins used to disperse pigments include acrylic resins and polyurethane resins.

[0291] [Pattern Layer]

[0292] A pattern layer is a layer that imparts textures, patterns, logos, and designs such as wood grain, geometric patterns, and leather textures to an object. There are no particular limitations on the methods for forming a pattern layer; specific examples include known printing methods, known coating methods, die-cutting, and etching. Examples of printing methods include direct gravure printing, gravure offset printing, inkjet printing, laser printing, and screen printing. Examples of coating methods include gravure coating, roller coating, die coating, bar coating, and blade coating.

[0293] In addition, the material for the pattern layer can be a film formed from the above-mentioned film forming composition, or a film or sheet formed from other resins, or a metal foil.

[0294] <Substrate Layer>

[0295] The substrate layer serves as a support layer for the decorative layer. Additionally, it acts as a protective layer, providing uniform elongation during molding and more effectively protecting the structure from external punctures, impacts, etc. The substrate layer can consist of a single layer or multiple layers. When the substrate layer is formed of multiple layers, the composition, shape, and thickness of the multiple layers can be the same or different from each other, and the combination of the multiple layers is not particularly limited as long as it does not impair the effect of the invention.

[0296] The substrate layer is not particularly limited, and examples include layers formed from materials such as resin, metal (steel plate, surface-treated steel plate, etc.), wood, and inorganic materials (glass, etc.), as well as layers formed from the aforementioned film-forming composition. Examples of resins include acrylic resins including polymethyl methacrylate, polyurethane, polyvinyl chloride, polycarbonate, polyolefins, polyesters, acrylonitrile-butadiene-styrene copolymers, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, and ethylene-vinyl acetate copolymers. Examples of polyolefins include polyethylene and polypropylene. Examples of polyesters include polyethylene terephthalate and polyethylene naphthalate.

[0297] The thickness of the substrate layer is not particularly limited. From the viewpoint of not adversely affecting the formability of the decorative layer and imparting the aforementioned function of the substrate layer to the film, it is preferably 2 μm or more and 500 μm or less, more preferably 5 μm or more and 200 μm or less. It should be noted that the term "thickness of the substrate layer" as used here refers to the overall thickness of the substrate layer. For example, the thickness of a substrate layer formed by multiple layers refers to the total thickness of all layers constituting the substrate layer.

[0298] <Adhesive Layer>

[0299] The film laminate of this embodiment may also include an adhesive layer between the substrate layer and the decorative layer. When the substrate layer and the decorative layer are formed by multiple layers, an adhesive layer may also be included between these layers. The adhesive layer may consist of a single layer or multiple layers of two or more. When the adhesive layer is formed by multiple layers, the composition, shape, and thickness of the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

[0300] The adhesive contained in the adhesive layer is not particularly limited and can be any commonly used adhesive. Specifically, examples include solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives such as acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives.

[0301] The thickness of the adhesive layer is not particularly limited. From the viewpoint of not adversely affecting the formability of the decorative layer and imparting the function of the substrate layer to the film, it is preferably 2 μm or more and 200 μm or less, more preferably 5 μm or more and 100 μm or less. It should be noted that the term "thickness of the adhesive layer" as used here refers to the overall thickness of the adhesive layer. For example, the thickness of an adhesive layer formed by multiple layers refers to the total thickness of all layers constituting the adhesive layer.

[0302] Adhesive Resin Compositions

[0303] The adhesive resin composition of this embodiment contains the following component 1), or component 1) and 2).

[0304] 1) The polyisocyanate compositions described in the above-mentioned "Polyisocyanate Compositions";

[0305] 2) Contains active hydrogen compounds

[0306] The adhesive resin composition according to this embodiment, by containing the above-described polyisocyanate composition, provides an adhesive resin cured product with excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity. The term "adhesive resin cured product" as used herein refers to the product obtained by curing the adhesive resin composition of this embodiment. That is, in one embodiment, the present invention provides an adhesive resin cured product obtained by curing the above-described adhesive resin composition.

[0307] <Containing active hydrogen compounds>

[0308] As active hydrogen compounds, as described in the above-mentioned <Active Hydrogen Compounds>.

[0309] In addition to the polyisocyanate composition described above, the adhesive resin composition of this embodiment may also contain other crosslinking agent components.

[0310] <Other cross-linking agent components>

[0311] Other cross-linking agents include, for example, epoxy compounds, oxazoline compounds, melamine compounds, and carbodiimide compounds.

[0312] There are no particular restrictions on the epoxy compound used, as long as it is a resin having two or more epoxy groups in one molecule; known epoxy compounds can be used. Examples of epoxy compounds include bisphenol-type epoxy compounds obtained by adding epichlorohydrin to bisphenol, phenolic varnish-type epoxy compounds obtained by adding epichlorohydrin to phenolic varnish resin, and polyethylene glycol diglycidyl ether. This epoxy compound can be used after being dispersed in water as needed.

[0313] Examples of oxazoline compounds include polymeric compounds having at least two oxazoline groups on their side chains, and monomeric compounds having at least two oxazoline groups in one molecule.

[0314] Examples of melamine compounds include partially hydroxymethylated melamine resins and fully hydroxymethylated melamine resins obtained by reacting melamine with an aldehyde. Examples of aldehydes include formaldehyde and paraformaldehyde. Alternatively, substances obtained by partially or fully etherifying the hydroxymethyl groups of the hydroxymethylated melamine resin with an alcohol can also be used. Examples of alcohols used in etherification include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, and 2-ethylhexanol.

[0315] Specific examples of this melamine compound include Cymel 303, Cymel 323, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 380, Cymel 385, Cymel 212, Cymel 251, Cymel 254, and Mycoat 776 (all trade names) manufactured by Nihon Cytec Industries Inc. of Japan.

[0316] As a carbodiimide compound, it can be obtained, for example, by decarbonylating the isocyanate groups of a polyisocyanate compound. Commercially available carbodiimide compounds include, for example, CARBODILITE V-02, CARBODILITE V-02-L2, CARBODILITE V-04, CARBODILITE E-01, and CARBODILITE E-02 (all manufactured by Nisshinbo Co., Ltd., trade names).

[0317] From the perspective of operability and ease of film formation when coating the substrate, the adhesive resin composition of this embodiment can be used, for example, in the form of a coating liquid diluted with various solvents, water, etc. As solvents that can be used, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, and acetic acid solvents can be suitably selected according to the purpose and application. These solvents can be used alone or in combination of two or more.

[0318] The concentration of solid components in the adhesive resin composition of this embodiment is not particularly limited, but is preferably 10% by mass or more and 80% by mass or less relative to the total mass of the adhesive resin composition, more preferably 15% by mass or more and 60% by mass or less, further preferably 20% by mass or more and 50% by mass or less, and particularly preferably 25% by mass or more and 40% by mass or less.

[0319] <Purpose of Use>

[0320] Examples of applications for the adhesive resin composition of this embodiment include automobiles, building materials or home appliances, woodworking, and laminates for solar cells. In particular, optical components used in liquid crystal displays for home appliances such as televisions, computers, digital cameras, and mobile phones require the lamination of films and sheets of various adhered materials to perform various functions. Since sufficient adhesion between the films and sheets of various adhered materials is required, the adhesive resin composition of this embodiment is a preferred example of its application.

[0321] [Object to be glued]

[0322] Examples of substrates that can be used with the adhesive resin composition of this embodiment include: various metals such as glass, aluminum, iron, galvanized steel sheet, copper, and stainless steel; porous components such as mortar and stone; components coated with fluorine-containing coatings, urethane coatings, or acrylic urethane coatings; cured sealants such as silicone-based, modified silicone-based, and urethane-based sealants; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; films and sheets of resins such as polyester, acrylic, polycarbonate, cellulose triacetate, and polyolefins; UV-curable acrylic resin layers; and layers containing inks such as printing inks and UV inks. Preferably, films and sheets of resins such as polyester, acrylic, polycarbonate, cellulose triacetate, and polyolefins, or UV-curable acrylic resin layers, are used.

[0323] The following example describes a case where the adhered object is a polyester film.

[0324] Examples of polyester resins that can be used as the adherend in the adhesive resin composition of this embodiment include polyethylene terephthalate, polyethylene terephthalate, polyethylene butylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, and polyester resins obtained by copolymerizing diols such as diethylene glycol, neopentyl glycol, and polyalkylene glycols with dicarboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. Among these, it is preferable that the polyester resin primarily consists of at least one selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate, polyethylene butylene terephthalate, and polyethylene naphthalate. Furthermore, from the perspective of balancing physical properties and cost, polyethylene terephthalate is most preferred among these polyester resins. In addition, from the perspective of improving chemical resistance, heat resistance, mechanical strength, etc., these polyester films or polyester sheets are preferably biaxially stretched.

[0325] In addition, polyester resins can contain various additives as needed. Examples of additives include antioxidants, organic lubricants, antistatic agents, ultraviolet absorbers, and surfactants.

[0326] To achieve the required strength for use as an optical component, the thickness of the polyester film is preferably 10 μm or more and 400 μm or less, more preferably 20 μm or more and 300 μm or less, and even more preferably 30 μm or more and 200 μm or less. Furthermore, the thickness of the polyester sheet is not particularly limited, but is preferably 1 mm or more and 10 mm or less, more preferably 2 mm or more and 8 mm or less, and even more preferably 3 mm or more and 5 mm or less. In this specification, the thickness distinguishes between films and sheets; those with a thickness of 500 μm or less are defined as films, and those with a thickness exceeding 500 μm are defined as sheets.

[0327] <Instructions for use of adhesive resin compositions>

[0328] The method of using the adhesive resin composition of this embodiment will be described.

[0329] Examples of methods for using the adhesive resin composition of the present invention include, for example, a method comprising the following steps: applying the adhesive resin composition of this embodiment to at least one substrate; bonding the substrate coated with the adhesive resin composition to another substrate; and, as needed, heating the laminated substrate to bond it together.

[0330] Furthermore, in applications involving laminated films for optical components, methods such as the following can be cited: a method of pre-coating an adhesive composition of this embodiment as an easy-to-bond treatment layer onto a polyester film or the like that becoming the adherend, and then bonding another adherend after performing a heat treatment process; a method of further coating an adhesive resin composition of this embodiment onto a film having an easy-to-bond treatment layer and then bonding the two materials. The adhesive resin composition of this embodiment is effective when used in any of the above methods.

[0331] The method for applying the coating liquid containing the adhesive resin composition of this embodiment to a film or the like can be any known method. Examples include roller coating, gravure coating, roller brush coating, spray coating, air knife coating, and curtain coating. These methods can be used individually or in combination.

[0332] The coating amount of the coating liquid is not particularly limited, but is preferably 0.01 μm or more and 1 μm or less based on the thickness after drying, more preferably 0.02 μm or more and 0.5 μm or less, and even more preferably 0.04 μm or more and 0.3 μm or less.

[0333] In addition, inorganic particles such as silica and talc, as well as organic particles such as acrylic, carbamate, and polyester compounds, can be mixed into the coating solution. Surfactants, defoamers, preservatives, and antistatic agents can also be mixed into the coating solution.

[0334] The following example illustrates the method for forming a coating layer in the case of producing an easy-to-adhere polyester film.

[0335] The adhesive resin composition of this embodiment can be used as a crosslinking agent component for an easy-to-adhere treatment layer (i.e., an adhesive layer pre-formed on the film substrate for adhesion to the substrate) applied to the surface of a polyester film to improve the adhesion between the polyester film and various adherends. For example, when used for easy-to-adhere treated polyester films, the easy-to-adhere treatment layer is mainly formed by the following two methods. One method is the following online coating method: for a polyester film before crystal orientation is completed, a coating liquid containing the necessary components is applied to the substrate film and dried, then stretched at least in one direction, followed by heat treatment to complete the orientation of the polyester film. The second method is the following offline coating method: after manufacturing the polyester film, a coating liquid is applied to the film and then dried. Generally, from the viewpoint of manufacturing efficiency of forming the coating layer at the same time as manufacturing the polyester film, the online coating method is preferred.

[0336] (Manufacturing method of easily bondable polyester film)

[0337] A method for manufacturing an easy-to-adhere polyester film in which the adhesive resin composition of this embodiment forms an easy-to-adhere treatment layer will be described.

[0338] First, the polyester to be formed into a film is melt-extruded in a film form, and then cooled and solidified to obtain an unstretched polyester film. For biaxially oriented polyester films, the unstretched film is stretched along its length at a temperature of Tg~(Tg+50)℃ to a ratio of 3 to 5 times, and then stretched along its width at a ratio of 3 to 5 times, or stretched simultaneously in both the length and width directions. This is followed by a heat treatment process at a temperature of 140℃ to 230℃ for a period of 1 second to 60 seconds to complete the process.

[0339] Conventionally, the heat treatment process involves a thermal process at 200°C for approximately one minute. From the perspective of protecting the environment and improving productivity, it is desirable to reduce the heat treatment process to a lower temperature. Therefore, a lower temperature approach of approximately 150°C for one minute was investigated as the thermal process. When using conventional adhesive compositions as easily bondable treatment layers, there is a decrease in initial adhesion and adhesion after damp heat testing. Therefore, it is strongly desired that adhesive compositions exhibit both initial adhesion and adhesion after damp heat testing in a lower temperature heat treatment process. To exhibit adhesion through a heat treatment process of approximately 150°C for one minute, it is preferable to form crosslinks at a lower temperature compared to end-capped polyisocyanates. Specifically, a crosslinking agent that can crosslink at temperatures below 60°C (the crosslinking reaction begins below 60°C) is preferred.

[0340] The formation of an easily bondable polyester film based on the adhesive resin composition of this embodiment can be carried out at any stage. Preferably, after applying the aforementioned coating liquid without stretching or after unidirectional stretching and drying, the film is stretched at least in one direction, followed by heat treatment. Furthermore, the coating liquid can be applied to only one side or to both sides, which is also acceptable.

[0341] Compositions for Coatings

[0342] The coating composition of this embodiment contains the following component 1), or component 1) and 2).

[0343] 1) The polyisocyanate compositions described in the above-mentioned "Polyisocyanate Compositions";

[0344] 2) Contains active hydrogen compounds

[0345] According to the coating composition of this embodiment, by containing the above-described polyisocyanate composition, a cured coating with excellent solvent resistance and good pot life can be provided. The term "cured coating" as used herein refers to a product obtained by curing the coating composition of this embodiment. That is, in one embodiment, the present invention provides a cured coating obtained by curing the above-described coating composition.

[0346] <Containing active hydrogen compounds>

[0347] As active hydrogen compounds, as described in the above-mentioned <Active Hydrogen Compounds>.

[0348] In addition, the coating composition of this embodiment may contain other crosslinking agent components besides the polyisocyanate composition described above.

[0349] <Other cross-linking agent components>

[0350] Other crosslinking agent components are as described in the above-mentioned <Other Crosslinking Agent Components>.

[0351] From the perspective of operability and ease of film formation when applying to the substrate, the coating composition of this embodiment can be used, for example, in the form of a coating liquid diluted with various solvents, water, etc. As solvents that can be used, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, and acetic acid solvents can be suitably selected according to the purpose and application. These solvents can be used alone or in combination of two or more.

[0352] There is no particular limitation on the concentration of solid components in the coating composition. From the perspective of ease of viscosity adjustment, it is preferably 10% by mass or more and 90% by mass or less relative to the total mass of the coating composition, more preferably 25% by mass or more and 80% by mass or less, further preferably 35% by mass or more and 75% by mass or less, and particularly preferably 40% by mass or more and 70% by mass or less.

[0353] Coating compositions can be baked at any temperature to promote curing. As a recent trend, there is a demand for coating compositions that cure at lower temperatures to reduce equipment heat energy. From the viewpoint of excellent curing properties at low temperatures, the baking temperature is preferably in the range of 40°C or higher and 200°C or lower, more preferably 60°C or higher and 180°C or lower, even more preferably 80°C or higher and 160°C or lower, and particularly preferably 100°C or higher and 140°C or lower. By keeping the baking temperature within the above range, a coating film with excellent low-temperature drying properties and solvent resistance can be obtained.

[0354] <Purpose of Use>

[0355] While not limited to the following, the coating composition of this embodiment can be suitably used as a primer coating, intermediate coating, or topcoat coating. These coatings are used, for example, for coating objects formed from various materials using coating methods such as roller coating, curtain flow coating, spray coating, electrostatic coating, and rotary cup coating. Furthermore, they are useful as coatings that impart decorative properties, weather resistance, acid resistance, rust prevention, and crack resistance to pre-coated metals, including rust-resistant steel sheets, automobiles, and plastics. Additionally, urethane raw materials are useful as adhesives, elastomers, foams, and surface treatment agents. Examples of applications for the coating composition of this embodiment include automobiles, building materials or home appliances, woodworking, and laminates for solar cells.

[0356] [Object to be painted]

[0357] Materials that can be coated as the object of a coating composition include: glass; various metals such as aluminum, iron, galvanized steel, copper, and stainless steel; porous components such as wood, paper, mortar, and stone; components coated with fluorine-containing coatings, urethane coatings, or acrylic urethane coatings; cured sealant materials such as silicone-based cured products, modified silicone-based cured products, and urethane-based cured products; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; leathers such as natural leather and artificial leather; fibers such as plant fibers, animal fibers, carbon fibers, and glass fibers; films and sheets of resins such as nonwoven fabrics, polyester, acrylics, polycarbonate, cellulose triacetate, and polyolefins; UV-curable acrylic resin layers; and layers containing inks such as printing inks and UV inks.

[0358] Example

[0359] The present embodiment will be further described in detail below based on examples and comparative examples. The present embodiment is not limited by the following examples. It should be noted that unless otherwise stated, "%" and "parts" in the text refer to mass.

[0360] The methods for determining the physical properties of the polyisocyanate compositions obtained in the synthesis examples, and the methods for evaluating the films and film laminates obtained in the examples and comparative examples are shown below.

[0361] <Methods for Determining and Evaluating Physical Properties>

[0362] [Physical Property 1] Viscosity

[0363] The measurements were taken at 25°C using an EMILA rotational viscometer.

[0364] [Physical Property 2] Number Average Molecular Weight

[0365] The number-average molecular weight is the number-average molecular weight of polystyrene as a reference, determined by gel permeation chromatography (GPC) using the apparatus described below. A polyisocyanate composition was used as the sample. The determination conditions are shown below.

[0366] (Measurement conditions)

[0367] Device: Made by Tosoh Corporation, HLC-802A

[0368] Column: Made by Tosoh Corporation, G1000HXL×1

[0369] G2000HXL × 1 piece

[0370] G3000HXL × 1 piece

[0371] Support: Tetrahydrofuran

[0372] Test method: Differential refractometer

[0373] [Physical Property 3] Isocyanate group (NCO) content

[0374] The isocyanate group (NCO) content was determined using the following method. It should be noted that when the polyisocyanate composition contains capped polyisocyanates, the capping agent is dissociated by heating or other means before being used as the test sample.

[0375] First, accurately weigh 2 g but less than 3 g (Wg) of the polyisocyanate composition into a flask. Next, add 20 mL of toluene to dissolve the polyisocyanate composition after decapping. Then, add 20 mL of a toluene solution containing 2 equivalents of di-n-butylamine, mix, and let stand at room temperature for 15 minutes. Next, add 70 mL of isopropanol and mix. Then, titrate this liquid with 1 equivalent of hydrochloric acid solution (factor F) to an indicator. Set the resulting titration value as V2 mL. Next, perform the same operation without the polyisocyanate composition, and set the resulting titration value as V1 mL. Then, calculate the isocyanate group (NCO) content of the polyisocyanate composition after decapping using the following formula: (Isocyanate group (NCO) content) × 1 (mass %).

[0376] Isocyanate group (NCO) content X1 (mass%) =

[0377] (V1-V2)×F×42 / (W×1000)×100

[0378] [Physical Property 4] Average number of total isocyanate groups

[0379] The average total number of isocyanate groups (average total number of NCO groups) is calculated using the following mathematical formula. In the case where the polyisocyanate composition contains capped polyisocyanates, "Mn" in the following formula represents the number-average molecular weight of the polyisocyanate composition measured after dissociation of the capping agent by heating or the like. In the case where the polyisocyanate composition contains capped polyisocyanates, "NCO content" is the percentage of isocyanate groups present relative to the total mass of the polyisocyanate composition, measured after dissociation of the capping agent by heating or the like, using X1 (mass %) calculated in "Physical Property 3" above. Furthermore, to convert the NCO content from a percentage to a decimal, the NCO content is multiplied by "0.01". "42" represents the formula weight of the isocyanate.

[0380] Total average NCO content = (Mn × NCO content (X1) × 0.01) / 42

[0381] [Property 5] End Capping Rate

[0382] The capping ratio in the polyisocyanate composition and the film-forming composition is determined by the following formula.

[0383] Capping rate = number of moles of capping agent / number of moles of isocyanate groups

[0384] It should be noted that the "molar number of isocyanate groups" in the above formula refers to the number of molar isocyanate groups per unit mass of the polyisocyanate composition after the end-capping agent has been dissociated through heat treatment. The NCO content (X1) calculated in "Physical Property 3" above is quantified using the following formula. Here, the NCO content (X1) is multiplied by "0.01" to convert the percentage to a decimal. "42" is the formula weight of isocyanate.

[0385] Molar number of isocyanate groups = (X1 × 0.01) / 42

[0386] In addition, the "molar number of capping agent" in the above formula refers to the number of capping agents captured during dissociation and quantified by gas chromatography-mass spectrometry analysis.

[0387] [Physical Property 6] Content of partially capped polyisocyanates

[0388] The content of partially capped polyisocyanates was determined by the following LC-MS and calculated using the formula shown below as a ratio of peak height.

[0389] Content of partially capped polyisocyanates =

[0390] [(peak B + peak C) / (peak A + peak B + peak C + peak D)] × 100

[0391] (Preprocessing)

[0392] Prepare a methanol solution (10 mg / mL) of the polyisocyanate composition and let it stand for 1 day.

[0393] (Using equipment)

[0394] ·LC: Agilent Technologies 1100 series

[0395] MS: LCQ manufactured by Thermo Electron

[0396] • Column: Phenomenex, Kinetex 2.6μm XB-C18 100A (2.1mm I.D. × 50mm)

[0397] (LC test conditions)

[0398] Column temperature: 40℃

[0399] • Detection: 205nm

[0400] • Flow rate: 0.35 mL / min

[0401] • Mobile phase: Use 0.05% formic acid aqueous solution as mobile phase A and methanol as mobile phase B.

[0402] • Gradient conditions: Set to 0 minutes, mobile phase A / mobile phase B = 50 / 50; 30 minutes, mobile phase A / mobile phase B = 0 / 100; 30.1 minutes, mobile phase A / mobile phase B = 50 / 50; 42 minutes, mobile phase A / mobile phase B = 50 / 50.

[0403] Injection volume: 2 μL / MS

[0404] (MS conditions)

[0405] • Ionization: APCI

[0406] • Pattern: Positive

[0407] • Scan range: m / Z = 250~2000

[0408] (Measurement Results)

[0409] In this assay, uncapped isocyanate groups were detected as peaks A through D between retention times of 16.4 and 18.4 minutes, in the form of addition to methanol.

[0410] Peak A: In the case of uncapped polyisocyanate trimer, methanol reacts with 3 isocyanate groups, and peak A, with a molecular weight of 600, is detected.

[0411] • Peak B: In the case of a single-terminated polyisocyanate trimer, a peak of the type in which methanol is added to two of the three isocyanate groups and a capping agent is added to one of the isocyanate groups is obtained. When the capping agent is 3,5-dimethylpyrazole, peak B with a molecular weight of 664 is detected.

[0412] • Peak C: In the case of a two-terminated polyisocyanate trimer, a peak of the type in which methanol is added to one of the three isocyanate groups and a capping agent is added to the other two isocyanate groups is obtained. When the capping agent is 3,5-dimethylpyrazole, a peak C with a molecular weight of 728 is detected.

[0413] Peak D: In the fully capped polyisocyanate trimer, a capping agent is added to the three isocyanate groups. When the capping agent is 3,5-dimethylpyrazole, peak D with a molecular weight of 792 is detected.

[0414] [Fabrication of one-time curing film F1]

[0415] The film-forming compositions obtained in the examples and comparative examples were applied to polypropylene (PP) sheets using a bar coater to achieve a resin film thickness of 60 μm, and then cured at 90°C for 30 minutes. Afterwards, the films were peeled off from the PP sheets to obtain a one-time cured film F1.

[0416] [Preparation of one-time curing film F1′]

[0417] The film-forming compositions obtained in the examples and comparative examples were applied to polypropylene (PP) sheets using a bar coater to achieve a resin film thickness of 60 μm, and then cured at 140°C for 30 minutes. The cured film F1′ was then peeled off from the PP sheet.

[0418] [Evaluation 1] Tensile properties

[0419] (1) Determination of the glass transition temperature of thin films

[0420] The film-forming compositions obtained in the examples and comparative examples were coated onto stainless steel plates using a rod coater to achieve a resin film thickness of 25 μm. The plates were then cured at 90°C for 30 minutes to obtain test pieces for glass transition temperature determination. The logarithmic decay rate of the obtained test pieces was measured using a rigid pendulum viscoelasticity meter (A&D Company, Limited, RPT-3000W). The peak of the temperature-logarithmic decay rate curve was taken as the glass transition temperature of the film. Based on the glass transition temperature obtained through this measurement, the measurement temperatures for elongation at break and fracture stress were determined.

[0421] (2) Determination of elongation at break and fracture stress

[0422] Tensile tests were conducted on films made from the film-forming compositions obtained in the Examples and Comparative Examples using a universal testing machine (A&D Company, Limited, RTE-1210) under the conditions shown below. Based on the elongation at break and tensile strength obtained by measurement, the elongation at break and tensile stress of the films were evaluated according to the following evaluation criteria.

[0423] (Measurement conditions)

[0424] Test piece dimensions: 10mm width × 20mm length

[0425] Test piece thickness: approximately 60 μm

[0426] Stretching speed: 20mm / minute

[0427] Measurement temperature: the measured glass transition temperature +10℃

[0428] (Evaluation criteria for elongation at break)

[0429] ☆: The elongation at break of the film at the test temperature is ≥200%.

[0430] ◎: The elongation at break of the film at the test temperature is ≥180% and ≤199%.

[0431] ○: The elongation at break of the film at the test temperature is ≥150% and ≤179%.

[0432] △: The elongation at break of the film at the measurement temperature is 50% or more and 149% or less.

[0433] ×: The elongation at break of the film at the test temperature is less than 50%.

[0434] (Evaluation criteria for fracture stress)

[0435] ☆: The tensile stress of the thin film at the test temperature is above 1.30 MPa.

[0436] ◎: The tensile stress of the thin film at the test temperature is above 1.10 MPa and below 1.29 MPa.

[0437] ○: The tensile stress of the thin film at the test temperature is above 0.80 MPa and below 1.09 MPa.

[0438] △: The fracture stress of the thin film at the measurement temperature is above 0.50 MPa and below 0.79 MPa.

[0439] ×: The fracture stress of the thin film at the test temperature is less than 0.50 MPa.

[0440] [Evaluation 2] Resistance to adhesion

[0441] The adhesiveness of each film made from the film-forming compositions obtained in the examples and comparative examples was confirmed by touch. Anti-adhesion was evaluated according to the evaluation criteria shown below. It should be noted that "adhesion" as used here refers to the property of adhesion known as instantaneous adhesive force; specifically, it can be described as the resistance when peeling off objects immediately after they are sandwiched between fingers.

[0442] (Evaluation Criteria)

[0443] ○: No adhesion detected

[0444] △: The stickiness has been slightly confirmed, but not to the extent that it will hinder its practicality.

[0445] ×: Significant viscosity confirmed.

[0446] [Preparation of secondary curing film]

[0447] (Using a secondary curing film F2 based on a primary curing film F1)

[0448] The thin film forming compositions obtained in the examples and comparative examples were coated onto a glass plate with a resin film thickness of 60 μm using a rod coater, and then heated and cured at 90°C for 30 minutes to obtain a one-time cured film F1.

[0449] The obtained primary cured film F1 is further cured by heating at 140°C for 30 minutes to obtain the secondary cured film F2.

[0450] (Using a secondary curing film F2′ using a first-cured film F1′)

[0451] The thin film forming compositions obtained in the examples and comparative examples were coated onto a glass plate with a resin film thickness of 60 μm using a rod coater, and then cured at 140°C for 30 minutes to obtain a one-time cured film F1′.

[0452] The cumulative light intensity after irradiation for 5 minutes on the side of the obtained primary cured film F1′ is 900 mJ / cm². 2 The secondary curing film F2′ is obtained by exposing it to ultraviolet light.

[0453] [Evaluation 3] Solvent resistance of the thin film laminate

[0454] Xylene (0.1 mL) was added to the surface of each film laminate prepared with the film-forming composition obtained in the usage examples and comparative examples. The state of the film was then visually observed after standing for 15 minutes to evaluate solvent resistance. The evaluation criteria are as follows.

[0455] (Evaluation Criteria)

[0456] ○: No roughness or marks were detected on the surface.

[0457] △: Some traces were slightly visible on the surface, but not enough to impair its usability.

[0458] ×: Obvious roughness and marks were observed on the surface.

[0459] [Preparation of adhesive resin cured products (laminated polyester boards)]

[0460] As the polyester sheet, polyethylene terephthalate sheet (product name: SUPERPET PLATE PET-6010, film thickness: 4mm) manufactured by Takiron Corporation was used.

[0461] On the surface of the aforementioned polyethylene terephthalate (PET) sheet, a coating liquid containing the adhesive resin composition obtained in the examples and comparative examples, with the resin solids content adjusted to 30% by mass, was applied using a coater and dried at 90°C for 30 seconds. This was followed by a heat treatment process at 150°C for 1 minute, and then cooling, to obtain an easily bonded polyester sheet with an easily bonded treatment layer having a film thickness of 1 μm.

[0462] Next, apply a UV-curable acrylic resin composition with the following components to the easily bondable surface using an applicator, and irradiate it with a UV lamp from the side of the board for 5 minutes, with a cumulative light intensity of 900 mJ / cm². 2The material is exposed to ultraviolet light and then subjected to a heat treatment at 150°C for 10 minutes to obtain a laminated polyester board with a 20μm thick ultraviolet-cured acrylic resin layer.

[0463] (Composition of UV-curable acrylic resin composition)

[0464] ·2,2-Bis(4-(acryloyloxydiethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., product name NKESTER A-BPE-4): 50% by mass relative to the total mass of the UV-curable acrylic resin composition.

[0465] Tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemicals Co., Ltd., product name VISCOAT#150): 40% by mass relative to the total mass of the UV-curable acrylic resin composition.

[0466] • (Manufactured by Ciba Specialty Chemicals, product name Irgacure 184): 10% by mass relative to the total mass of the UV-curable acrylic resin composition.

[0467] [Evaluation 4] Solvent resistance before lamination

[0468] As the polyester sheet, polyethylene terephthalate sheet (product name: SUPERPET PLATE PET-6010, film thickness: 4mm) manufactured by Takiron Corporation was used.

[0469] On the surface of the aforementioned polyethylene terephthalate (PET) sheet, a coating liquid containing the adhesive resin composition obtained in the examples and comparative examples, with the resin solids content adjusted to 30% by mass, was applied using a coater and dried at 90°C for 30 seconds. This was followed by a heat treatment process at 150°C for 1 minute, and then cooling, to obtain an easily bonded polyester sheet with an easily bonded treatment layer having a film thickness of 1 μm.

[0470] On the obtained easily bonded polyester board, toluene was added to a 1 cm diameter silicone ring, and a petri dish was placed on top. The mixture was then left to stand at 23°C for 2 hours. Afterward, the toluene was wiped off with Kimwipes, and the coating condition was checked. The solvent resistance before lamination was evaluated according to the following evaluation criteria.

[0471] (Evaluation Criteria)

[0472] 5: Almost no change

[0473] 4: A faint trace is visible within a 1cm ring.

[0474] 3: A clear mark appears in a 1cm ring.

[0475] 2: Partial deterioration occurs inside the 1cm ring.

[0476] 1: Overall deterioration occurred within a 1cm ring.

[0477] [Evaluation 5] Fit with the upper layer

[0478] On the UV-curable acrylic resin layer of the obtained laminated polyester board, 100 checkerboard-shaped cuts were made using a cutting guide with 2mm gaps, penetrating only the UV-curable acrylic resin layer. Transparent tape (made by NICHIBAN CO.,LTD, No. 405, 24mm wide) was then applied to the checkerboard-shaped cut surfaces and rubbed with an eraser to ensure complete adhesion. The transparent tape was then rapidly peeled off from the UV-curable acrylic resin layer of the laminated polyester board at a 180° peel angle. The peeled surface was observed, and the number of peeled checkerboard squares was counted. Adhesion to the upper layer was evaluated according to the following evaluation criteria.

[0479] (Evaluation Criteria)

[0480] 5: The number of chessboard squares removed is 0.

[0481] 4: Only a portion of the edge of the checkerboard pattern was peeled off.

[0482] 3: The number of chessboard squares removed is between 1 and 10.

[0483] 2: The number of chessboard squares removed is between 11 and 20.

[0484] 1: The number of chessboard squares removed is 21 or more.

[0485] [Evaluation 6] Stability under high temperature and high humidity

[0486] The obtained laminated polyester sheets were placed in a high-temperature, high-humidity bath at 80°C and 95% RH for 48 hours. Afterward, the laminated polyester sheets were removed and placed at room temperature for 10 hours. The adhesion was then evaluated using the same method as the initial adhesion evaluation. The evaluation criteria are as follows.

[0487] (Evaluation Criteria)

[0488] 5: The number of chessboard squares removed is 0 (including cases where only the edges are removed).

[0489] 4: The number of chessboard squares removed is between 1 and 15.

[0490] 3: The number of chessboard squares removed is between 16 and 30.

[0491] 2: The number of chessboard squares removed is between 31 and 50.

[0492] 1: The number of chessboard squares removed is 51 or more.

[0493] [Evaluation of the coating]

[0494] [Evaluation 7] Low-temperature drying properties

[0495] The coating compositions obtained in the examples and comparative examples were coated onto polypropylene boards, baked at 120°C for 30 minutes, and then cut out. The coatings were then placed in acetone at 23°C for 24 hours. The impregnated coatings were dried, and the percentage of residual coating was calculated from the weight before acetone impregnation to evaluate the retention rate. The evaluation criteria are as follows.

[0496] (Evaluation Criteria)

[0497] ◎: Survival rate of over 90%

[0498] ○: The survival rate is above 80% but less than 90%.

[0499] ×: Survival rate less than 80%

[0500] [Evaluation 8] Solvent resistance of the coating film

[0501] The coating compositions obtained in the examples and comparative examples were coated onto glass plates, baked at 120°C for 30 minutes, and then placed at 23°C and 50% humidity for 24 hours. For this coating film, a rubbing test was performed by rubbing a cotton cloth impregnated with acetone back and forth 20 times. The appearance of the coating film was visually observed and evaluated. The evaluation criteria are as follows.

[0502] (Evaluation Criteria)

[0503] ◎: Almost no change is visible on the coating.

[0504] ○: A few traces can be seen on the coating.

[0505] ×: Dissolution marks are visible on the coating.

[0506] [Evaluation 9] Pot life of coating

[0507] After preparing the coating compositions obtained in the examples and comparative examples, the viscosity increase rate at 25°C (with the initial viscosity as 100%) after storage at 23°C for 7 hours was evaluated. The evaluation criteria are as follows.

[0508] (Evaluation Criteria)

[0509] ◎: Viscosity increase rate is 100% or more but less than 150%

[0510] ○: Viscosity increase rate is 150% or more but less than 180%

[0511] △: Viscosity increase rate is 180% or more but less than 200%

[0512] ×: Viscosity increase rate is over 200%

[0513] Synthesis of Polyisocyanates

[0514] [Synthetic Example 1] (Synthesis of polyisocyanate p-1)

[0515] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 600 parts of HDI and 30 parts of a polyester polyol derived from triol and ε-caprolactone (manufactured by Daicel Co., Ltd., trade name "PLACCEL 303") were added. The urethane esterification reaction was carried out by maintaining the reactor temperature at 90°C for 1 hour with stirring. The reactor temperature was then maintained at 60°C, and tetramethyldecanoate ammonium, an isocyanurate esterification catalyst, was added. Phosphoric acid was added at the point where the specified yield was reached to stop the reaction. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator. The number-average molecular weight of the reaction products was determined by GPC, and the isocyanate content was determined by titration, thus confirming the formation of polyisocyanates. The obtained polyisocyanate p-1 had a viscosity of 9,500 mPa·s at 25 °C, an isocyanate content of 19.2%, a number-average molecular weight of 1,100, and an average isocyanate base number of 5.3.

[0516] [Synthetic Example 2] (Synthesis of polyisocyanate p-2)

[0517] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 600 parts of HDI were added, and the reactor temperature was maintained at 60°C. Tetramethyldecanoate ammonium, an isocyanurate esterification catalyst, was added. The reaction was stopped by adding phosphoric acid when the isocyanate content in the reaction solution reached 38.7% by mass. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator. The number-average molecular weight of the reaction products was determined by GPC, and the isocyanate content was determined by titration, thus confirming the formation of polyisocyanates. The resulting polyisocyanate p-2 had a viscosity of 2,700 mPa·s at 25°C, an isocyanate content of 21.7%, a number-average molecular weight of 660, and an average isocyanate basis of 3.4.

[0518] [Synthetic Example 3] (Synthesis of polyisocyanate p-3)

[0519] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 700 parts HDI, 300 parts IPDI, and 30 parts of PLACEL 303 (a trade name from Daicel Chemicals, molecular weight 300), a polycaprolactone-based polyester polyol, were added. The urethane esterification reaction was carried out by maintaining the reactor temperature at 90°C for 1 hour with stirring. The reactor temperature was then maintained at 80°C, and tetramethyldecanoate ammonium, an isocyanurate esterification catalyst, was added. The reaction was stopped by adding phosphoric acid when the isocyanate content of the reaction solution reached 36.2% by mass. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator. The number-average molecular weight of the reaction products was determined by GPC, and the isocyanate content was determined by titration to confirm the formation of polyisocyanates. The obtained polyisocyanate p-3 had a viscosity of 180,000 mPa·s at 25 °C, an isocyanate content of 18.7%, a number-average molecular weight of 1200, and an average isocyanate base number of 5.3.

[0520] [Synthetic Example 4] (Synthesis of polyisocyanate p-4)

[0521] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 1000 parts of HDI and 340 parts of a polyester polyol derived from triol and ε-caprolactone (manufactured by Daicel Co., Ltd., trade name "PLACCEL 308") were added. The urethane esterification reaction was carried out by maintaining the reactor temperature at 95°C for 1.5 hours with stirring. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator. The number-average molecular weight of the reaction products was determined by GPC, and the isocyanate content was determined by titration to confirm the formation of polyisocyanates. The resulting polyisocyanate p-4 had a viscosity of 4,000 mPa·s at 25°C, an isocyanate content of 9.1%, a number-average molecular weight of 1,500, and an average isocyanate basis of 3.2.

[0522] [Table 1-1]

[0523] Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Polyisocyanates p-1 p-2 p-3 p-4 NCO total average 5.3 3.4 5.3 3.2 Number average molecular weight 1100 660 1200 1500

[0524] <(1-1) Preparation of Polyisocyanate Compositions>

[0525] [Example 1-1-5]

[0526] (Preparation of the polyisocyanate composition PI-a1-1)

[0527] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 500 g of polyisocyanate p-1 and 200 g of butyl acetate obtained in Synthesis Example 1 were added. The mixture was heated to 60°C with stirring, and 0.75 molar amounts of 3,5-dimethylpyrazole (hereinafter sometimes referred to as "3,5-DMP") as a capping agent were slowly added as a proportion relative to the isocyanate groups in polyisocyanate p-1. After all the contents were added, the mixture was stirred for another 1 hour to obtain the polyisocyanate composition PI-a1-1.

[0528] [Comparative Example 1-3-1]

[0529] (Preparation of the polyisocyanate composition PI-b1-1)

[0530] The polyisocyanate p-1 synthesized in Synthesis Example 1 was diluted with butyl acetate in such a way that the solid content was 75% by mass relative to the total mass of the composition, to obtain the polyisocyanate composition PI-b1-1.

[0531] [Comparative Example 1-3-2]

[0532] (Preparation of the polyisocyanate composition PI-b1-2)

[0533] The amount of 3,5-dimethylpyrazole added was set to be 1.05 times the molar amount of the isocyanate group of the polyisocyanate. Otherwise, the polyisocyanate composition PI-b1-2 was obtained using the same method as in Example 1.

[0534] [Example 1-1-3]

[0535] (Preparation of the polyisocyanate composition PI-a1-3)

[0536] The polyisocyanate composition PI-b1-1 obtained in Comparative Example 1-3-1 and the polyisocyanate composition PI-b1-2 obtained in Comparative Example 1-3-2 were mixed at a molar ratio of isocyanate groups of 1:1 (including end-capped isocyanate groups) to obtain the polyisocyanate composition PI-a1-3.

[0537] [Examples 1-1-1, 1-1-2, 1-1-4, 1-1-6 to 1-1-11]

[0538] (Polyisocyanate compositions PI-a1-1, PI-a1-2, PI-a1-4, PI-a1-6 to PI-a1-11)

[0539] The types of polyisocyanates and capping agents used, the capping rates, and the content (mol%) of partially capped polyisocyanates are as described in Table 1-2, except that the polyisocyanate compositions PI-a1-1, PI-a1-2, PI-a1-4, PI-a1-6 to PI-a1-11 were obtained using the same method as in Examples 1-1-5. It should be noted that in Table 1-2, "3,5-DMP" refers to 3,5-dimethylpyrazole, "MEK-Ox" refers to methyl ethyl ketone oxime, "ε-CL" refers to ε-caprolactam, and "DEM" refers to diethyl malonate (the same applies hereinafter).

[0540] [Table 1-2]

[0541]

[0542] <(1-2) Preparation of the composition for thin film formation>

[0543] (Preparation of active hydrogen compounds AH-1-1 to AH-1-5)

[0544] Prepare ethyl acetate solutions of acrylic polyol resins (AP), polycaprolactone diol resins (PCL-1, PCL-2), and polycarbonate diol resins (PCD). The hydroxyl concentration (resin basis), solids content, and solvents used for these resins are shown in Tables 1-3.

[0545] The above resins were mixed according to the proportions recorded in Table 1-4 to obtain active hydrogen compounds AH-1-1 to AH-1-5.

[0546] [Table 1-3]

[0547]

[0548] [Table 1-4]

[0549]

[0550] [Example 1-2-1]

[0551] (Preparation of thin film forming composition F-a1)

[0552] The polyisocyanate composition PI-a1-3 obtained in Examples 1-1-3 was combined with an active hydrogen compound AH-1-1 in a manner with NCO / OH = 1.0, and diluted with propylene glycol-1-monomethyl ether-2-acetate (PMA) to a solid content of 25% by mass. At this time, dibutyltin dilaurate was added at a concentration of 0.1% relative to the resin to obtain a film forming composition F-a1.

[0553] [Examples 1-2-2 to 1-2-15]

[0554] (Preparation of thin film forming compositions F-a2 to F-a15)

[0555] The compositions containing active hydrogen compounds and polyisocyanates were prepared as described in Tables 1-5, except that the thin film forming compositions F-a2 to F-a15 were obtained using the same method as in Example 1-2-1.

[0556] [Comparative Example 1-4-1]

[0557] (Preparation of thin film forming composition F-b1)

[0558] The polyisocyanate composition PI-b1-1 obtained in Comparative Example 1-3-1 was used as the polyisocyanate composition, and the composition for film formation was otherwise obtained using the same method as in Example 1-2-2.

[0559] [Comparative Example 1-4-2]

[0560] (Preparation of thin film forming composition F-b2)

[0561] The polyisocyanate composition PI-b1-2 obtained in Comparative Example 1-3-2 was used as the polyisocyanate composition, and the film forming composition F-b2 was otherwise obtained using the same method as in Example 1-2-2.

[0562] <(1-3) Manufacturing of primary curing film F1 and secondary curing film F2>

[0563] Using the methods described above for preparing a single-cured film F1 and a film laminate using the single-cured film F1, single-cured film F1 and double-cured film F2 were prepared using the film-forming compositions manufactured in the Examples and Comparative Examples, and the films were evaluated. The evaluation results are shown in Tables 1-5 below. The film using the film-forming composition F-b2 manufactured in Comparative Example 1-4-2 was brittle and could not be cut into test pieces for measuring elongation at break and fracture stress. Therefore, it is marked as "cannot be measured" in Tables 1-5.

[0564] [Table 1-5]

[0565]

[0566] According to Tables 1-5, the films formed using the film forming compositions F-a1 to F-a15 of Examples 1-2-1 to 1-2-15 maintained good tensile strength and excellent anti-adhesion properties. In addition, the film laminates formed by laminating these films on a glass plate exhibited excellent solvent resistance.

[0567] Films using film-forming compositions F-a2, F-a5 to F-a15, which contain polyisocyanate compositions with high end-capping rates, show a tendency to exhibit particularly good elongation at break.

[0568] Furthermore, films using film-forming compositions F-a2, F-a5 to F-a7, and F-a9 to F-a15, which contain a polyisocyanate composition with an end-capping rate of 50 to 80 mol% and have a molar number γ of functional group X of the one-time cured film of 0.1 or more and 0.4 or less, tend to exhibit particularly good elongation at break and stress at break.

[0569] On the other hand, the films and film laminates using the film forming compositions F-b1 to F-b2 of Comparative Examples 1-4-1 and 1-4-2 did not achieve good tensile properties and excellent resistance to adhesion and solvents.

[0570] <(1-4) Preparation of the thin film forming composition and the one-time cured thin film F1′>

[0571] [Examples 1′-2-1~1′-2-2]

[0572] (Preparation of thin film forming composition F′-a1)

[0573] For the polyisocyanate composition PI-b1-1, a hydroxyl-containing polyester acrylate PEA-1 (hydroxyl concentration 1.21 wt%, acryloyl concentration 11.0 wt%) was formulated with an NCO / OH ratio of 1.0. Next, a photoinitiator Omnirad 651 (made from IGM resin) was added at 5 wt% relative to PEA-1. The mixture was then diluted with propylene glycol-1-monomethyl ether-2-acetate (PMA) to a solid content of 25 wt%. At this point, dibutyltin dilaurate was added at 0.1 wt% relative to the resin concentration to obtain a film-forming composition F′-a1.

[0574] (Preparation of thin film forming composition F′-a2)

[0575] The hydroxyl-containing polyester acrylate was changed to PEA-2 (hydroxyl concentration 2.12% by mass, acryloyl concentration 20.6% by mass), and the film-forming composition F′-a2 was otherwise obtained by the same method as F′-a1.

[0576] Following the above-described method for preparing a single-cured film F1′ and a method for preparing a film laminate using the single-cured film F1′, a single-cured film F1′ and a double-cured film F2′ were prepared using the film-forming compositions manufactured in the Examples and Comparative Examples, and the films were evaluated. The evaluation results are shown in Tables 1-6.

[0577] [Table 1-6]

[0578]

[0579] According to Tables 1-6, the films formed using the film forming compositions F-b1 to F-b4 of Examples 1-3-1 to 1-3-2 maintained good tensile properties and had excellent anti-adhesion properties. In addition, the film laminate obtained by laminating the films on a glass plate had excellent solvent resistance.

[0580] <(2-1) Preparation of Polyisocyanate Compositions>

[0581] [Example 2-1-1]

[0582] (Preparation of the polyisocyanate composition PI-a2-1)

[0583] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 500 g of polyisocyanate p-1 and 200 g of butyl acetate obtained in Synthesis Example 1 were added. The mixture was heated to 60°C with stirring, and 0.75 molar amounts of 3,5-dimethylpyrazole (hereinafter sometimes referred to as "3,5-DMP") as a capping agent were slowly added as a ratio of 0.75 molars relative to the isocyanate groups in polyisocyanate p-1. After all the contents were added, the mixture was stirred for another 1 hour to obtain the polyisocyanate composition PI-a2-1.

[0584] [Comparative Example 2-3-1]

[0585] (Preparation of the polyisocyanate composition PI-b2-1)

[0586] The polyisocyanate p-1 synthesized in Synthesis Example 1 was diluted with butyl acetate in such a way that the solid content was 75% by mass relative to the total mass of the composition, to obtain the polyisocyanate composition PI-b2-1.

[0587] [Comparative Example 2-3-2]

[0588] (Preparation of the polyisocyanate composition PI-b2-2)

[0589] The amount of 3,5-dimethylpyrazole added was set to be 1.05 times the molar amount of the isocyanate group of the polyisocyanate. Otherwise, the polyisocyanate composition PI-b2-2 was obtained using the same method as in Example 1.

[0590] [Comparative Example 2-3-3]

[0591] (Preparation of the polyisocyanate composition PI-b2-3)

[0592] The polyisocyanate composition PI-b2-3 was obtained by replacing 3,5-dimethylpyrazole with a mixture of MEK-Ox and 3,5-DMP (MEK-Ox / 3,5-DMP = 1 / 1 (molar ratio)) and setting the addition amount to 1.05 times the molar amount of the isocyanate groups of the polyisocyanate. Otherwise, the same method as in Example 1 was used.

[0593] [Example 2-1-2]

[0594] (Preparation of the polyisocyanate composition PI-a2-2)

[0595] The polyisocyanate composition PI-b2-1 obtained in Comparative Example 2-3-1 and the polyisocyanate composition PI-b2-2 obtained in Comparative Example 2-3-2 were mixed at a molar ratio of isocyanate groups of 1:1 (including end-capped isocyanate groups) to obtain the polyisocyanate composition PI-a2-2.

[0596] [Examples 2-1-3 to 2-1-11]

[0597] (Preparation of polyisocyanate compositions PI-a2-3 to PI-a2-11)

[0598] The types of polyisocyanates and capping agents used, the capping rates, and the content (mol%) of partially capped polyisocyanates are as described in Table 2-1. Otherwise, polyisocyanate compositions PI-a2-3 to PI-a2-11 were obtained using the same method as in Example 1. It should be noted that in Table 2-1, “MEK-Ox” represents methyl ethyl ketone oxime, and “ε-CL” represents ε-caprolactam (the same applies hereinafter).

[0599] [Table 2-1]

[0600]

[0601] <(2-2) Preparation of adhesive resin composition>

[0602] [Example 2-2-1]

[0603] (Preparation of adhesive resin composition S-a1)

[0604] Compared to the polyisocyanate composition PI-a2-1 obtained in Example 2-1-1, an ethyl acetate solution of an acrylic polyol resin (hydroxyl concentration 4.5% by mass (resin basis), resin solids content 41% by mass, hereinafter referred to as "AH-3") was prepared with NCO / OH = 1.0 and diluted with propylene glycol-1-monomethyl ether-2-acetate (PMA) to a solids content of 30% by mass to obtain an adhesive resin composition S-a1.

[0605] [Examples 2-2-2 to 2-2-11 and Comparative Examples 2-4-1 to 2-4-3]

[0606] (Adhesive resin compositions S-a2~S-a11 and S-b1~S-b3)

[0607] Assuming the polyisocyanate compositions listed in Table 2-2 are used, adhesive resin compositions S-a2 to S-a11 and S-b1 to S-b3 are obtained using the same method as in Example 2-2-1.

[0608] The adhesive resin compositions prepared in the Examples and Comparative Examples were evaluated using the methods described above. The results are shown in Tables 2-2 below.

[0609] [Table 2-2]

[0610]

[0611] According to Table 2-2, the adhesive resin cured products using adhesive resin compositions S-a1 to S-a11 (Examples 2-2-1 to 2-2-11) exhibit excellent solvent resistance before lamination, adhesion to the upper layer, and stability under high temperature and high humidity.

[0612] Furthermore, in the adhesive resin compositions S-a1 and S-a4 (Examples 2-2-1 and 2-2-4), S-a3 and S-a6 (Examples 2-2-3 and 2-2-6), in the case of adhesive resin compositions S-a4 and S-a6 (Examples 2-2-4 and 2-2-6) containing a polyisocyanate composition with a high end-capping rate, it is observed that the resulting cured adhesive resin tends to have better adhesion to the upper layer and better stability under high temperature and high humidity. On the other hand, in the case of adhesive resin compositions S-a1 and S-a3 (Examples 2-2-1 and 2-2-3) containing a polyisocyanate composition with a low end-capping rate, it is observed that the solvent resistance before lamination when preparing the cured adhesive resin tends to be better.

[0613] Furthermore, in the adhesive resin compositions S-a2 and S-a5 (Examples 2-2-2 and 2-2-5), in the case of adhesive resin composition S-a5 (Example 2-2-5) which contains a polyisocyanate composition with a higher content of partially capped polyisocyanate, it is observed that the solvent resistance before lamination, the adhesion to the upper layer, and the stability under high temperature and high humidity are superior when the adhesive resin is cured.

[0614] Furthermore, in adhesive resin compositions S-a5, S-a8 to S-a10 (Examples 2-2-5, 2-2-8 to 2-2-10), adhesive resin compositions S-a5 and S-a9 (Examples 2-2-5 and 2-2-9) containing polyisocyanate compositions with a larger average total number of isocyanate groups showed a tendency to exhibit superior stability under high temperature and high humidity conditions.

[0615] Furthermore, in the adhesive resin compositions S-a5, S-a7, and S-a11 (Examples 2-2-5, 2-2-7, and 2-2-11), in the case of adhesive resin composition S-a5 (Example 2-2-5) which contains a polyisocyanate composition using 3,5-DMP as a capping agent, it can be observed that the resulting cured adhesive resin tends to have better adhesion to the upper layer than in the other two examples.

[0616] On the other hand, the cured adhesive resins using adhesive resin compositions S-b1 to S-b3 (Comparative Examples 2-4-1 to 2-4-3) did not achieve excellent results in terms of solvent resistance before lamination, adhesion to the upper layer, and stability under high temperature and high humidity.

[0617] <(3-1) Preparation of Polyisocyanate Compositions>

[0618] [Example 3-1-1]

[0619] (Preparation of the polyisocyanate composition PI-a3-1)

[0620] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 500 g of polyisocyanate p-1 and 200 g of butyl acetate obtained in Synthesis Example 1 were added. The mixture was heated to 60°C with stirring, and 0.75 molar amounts of 3,5-dimethylpyrazole (hereinafter sometimes referred to as "3,5-DMP") as a capping agent were slowly added, relative to the molar amounts of isocyanate groups in polyisocyanate p-1. After all the contents were added, the mixture was stirred for another 1 hour to obtain the polyisocyanate composition PI-a3-1.

[0621] [Comparative Example 3-3-1]

[0622] (Preparation of the polyisocyanate composition PI-b3-1)

[0623] The polyisocyanate p-2 synthesized in Synthesis Example 2 was diluted with butyl acetate in such a way that the solid content was 75% by mass relative to the total mass of the composition, to obtain the polyisocyanate composition PI-b3-1.

[0624] [Comparative Example 3-3-2]

[0625] (Preparation of the polyisocyanate composition PI-b3-2)

[0626] The amount of 3,5-dimethylpyrazole added was set to be 1.05 times the molar amount of the isocyanate group of the polyisocyanate, and the polyisocyanate composition PI-b3-2 was obtained using the same method as in Example 1.

[0627] [Comparative Example 3-3-3]

[0628] (Preparation of the polyisocyanate composition PI-b3-3)

[0629] The polyisocyanate composition PI-b3-3 was obtained by replacing 3,5-dimethylpyrazole with a mixture of MEK-Ox and 3,5-DMP (MEK-Ox / 3,5-DMP = 1 / 1 (molar ratio)) and setting the addition amount to 1.05 times the molar amount of the isocyanate groups of the polyisocyanate. Otherwise, the same method as in Example 3-1-1 was used.

[0630] [Example 3-1-12]

[0631] (Preparation of the polyisocyanate composition PI-a3-12)

[0632] The polyisocyanate composition PI-b3-1 obtained in Comparative Example 3-3-1 and the polyisocyanate composition PI-b3-2 obtained in Comparative Example 3-3-2 were mixed at a molar ratio of isocyanate groups of 2:1 (including capped isocyanate groups) to obtain the polyisocyanate composition PI-a3-12.

[0633] [Examples 3-1-2 to 3-1-11]

[0634] (Preparation of polyisocyanate compositions PI-a3-2 to PI-a3-11)

[0635] The types of polyisocyanates and capping agents used, the capping rate, and the content (mol%) of partially capped polyisocyanates are as described in Table 3-1. Otherwise, the polyisocyanate compositions PI-a3-2 to PI-a3-11 were obtained using the same method as in Example 1.

[0636] [Table 3-1]

[0637]

[0638] <(3-2) Preparation of Coating Compositions>

[0639] [Example 3-2-1]

[0640] (Preparation of coating composition C-a1)

[0641] For the polyisocyanate composition PI-a3-1 obtained in Example 3-1-1, an acrylic polyol resin solvent naphtha solution (hydroxyl concentration 4.5% by mass (resin basis), resin solids content 65% by mass, hereinafter referred to as "AH-4") was mixed with butyl acetate to a solids content of 50% by mass to obtain the coating composition C-a1.

[0642] [Examples 3-2-2 to 3-2-12 and Comparative Examples 3-4-1 to 3-4-3]

[0643] (Coating compositions C-a2~C-a12 and C-b1~C-b3)

[0644] Assuming the polyisocyanate compositions listed in Table 3-2 are used, coating compositions C-a2 to C-a12 and C-b1 to C-b3 are obtained using the same method as in Example 3-2-1.

[0645] The coating compositions manufactured in the Examples and Comparative Examples were evaluated using the methods described above. The results are shown in Tables 3-2 below.

[0646] [Table 3-2]

[0647]

[0648] According to Table 3-2, the coating compositions using coating compositions C-a1 to C-a12 (Examples 3-2-1 to 3-2-12) exhibit excellent low-temperature drying properties, solvent resistance, and pot life.

[0649] Furthermore, in coating compositions C-a1 and C-a4, C-a5, C-a6 (Examples 3-2-1 and 3-2-4, 3-2-5, 3-2-6), coating compositions containing polyisocyanate compositions with higher end-capping rates tend to have a longer pot life. On the other hand, coating compositions C-a3 and C-a7, C-a8, C-a9, C-a10, C-a11, C-a12 (Examples 3-2-3 and 3-2-7, 3-2-8, 3-2-9, 3-2-10, 3-2-11, 3-2-12) containing polyisocyanate compositions with lower end-capping rates tend to have better low-temperature drying properties.

[0650] Furthermore, in coating compositions C-a2 and C-a3, C-a6, C-a7, C-a10, and C-a11 (Examples 3-2-2 and 3-2-3, 3-2-6, 3-2-7, 3-2-10, and 3-2-11), when the content of partially capped polyisocyanates is moderate to low, a tendency is observed in the obtained cured coatings to exhibit superior solvent resistance.

[0651] Furthermore, in coating compositions C-a7 and C-a12 (Examples 3-2-7 and 3-2-12), a tendency for the coating to have a longer pot life can be observed in the case of coating composition C-a7 (Example 3-2-7), which contains a polyisocyanate composition with the same end-capping rate but a higher ratio of partially end-capped polyisocyanates.

[0652] On the other hand, the cured coatings using coating compositions C-b1 to C-b3 (Comparative Examples 3-4-1 to 3-4-3) did not achieve excellent results in terms of low-temperature drying properties, solvent resistance, and pot life.

[0653] Industrial availability

[0654] The polyisocyanate composition according to this embodiment provides a polyisocyanate composition that, when used as a film-forming composition, maintains good tensile strength of the film and exhibits excellent resistance to adhesion and solvents; when used as an adhesive resin composition, it provides excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity; and when used as a coating composition, it balances the solvent resistance of the coating film and the shelf life of the coating. The film-forming composition according to this embodiment provides a film that maintains good tensile strength and exhibits excellent resistance to adhesion and solvents. The film and film laminate of this embodiment can be manufactured using the aforementioned film-forming composition and can be used as a decorative film suitable for articles made of various materials. The adhesive resin composition and cured adhesive resin of this embodiment can be manufactured using the aforementioned polyisocyanate composition, providing an adhesive resin cured product that exhibits excellent solvent resistance before lamination, excellent adhesion to various functional layers used as upper layers, and excellent stability under high temperature and high humidity. The coating composition and cured coating according to this embodiment can provide a cured coating with excellent solvent resistance and good pot life.

Claims

1. A one-time curing film, formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a backbone and an active hydrogen-containing compound. The primary cured film comprises: at least one functional group X selected from the group consisting of urethane groups, urea groups, and amide groups, generated by curing the active hydrogen compound and the polyisocyanate composition; an active hydrogen group; and isocyanate groups blocked by a capping agent. The ratio γ / β of the number of moles of functional group X contained in the primary cured film to the number of moles of isocyanate groups blocked by the end-capping agent is 0.1 or more and 9.0 or less. The active hydrogen-containing compound includes acrylic polyols.

2. The one-time cured film according to claim 1, wherein, The polyisocyanate composition contains a polyisocyanate having an isocyanurate structure.

3. The one-time cured film according to claim 1, wherein, The capping agent comprises any one of acid amide compounds, oxime compounds, active methylene compounds, or pyrazole compounds.

4. The primary cured film according to any one of claims 1 to 3, wherein, The capping agent comprises any one of methyl ethyl ketone oxime, ε-caprolactam, diethyl malonate, 3-methylpyrazole, or 3,5-dimethylpyrazole.

5. The one-time cured film according to claim 1, wherein, The γ / β ratio is greater than 0.1 and less than 2.

4.

6. The primary cured film according to any one of claims 1 to 3, wherein, The number of moles of functional group X γ contained in 1 kg of the primary cured film is 0.05 or more and 1.0 or less.

7. The primary cured film according to claim 6, wherein, The number of moles of functional group X γ contained in 1 kg of the primary cured film is 0.1 or more and 0.4 or less.

8. The primary cured film according to any one of claims 1 to 3, wherein, The active hydrogen-containing compound includes a diol.

9. The primary cured film according to any one of claims 1 to 3, wherein, The number of moles γ of functional group X contained in 1 kg of the primary cured film is 0.1 or more and 0.4 or less, and... The number of moles of functional group X γ' contained in 1 kg of secondary cured film is 0.5 or more and 1.2 or less.

10. The primary cured film according to any one of claims 1 to 3, wherein, The ratio γ / γ' of the number of moles of functional group X contained in 1 kg of the primary cured film to the number of moles of functional group X contained in 1 kg of the secondary cured film is 0.2 or more and 0.5 or less.

11. The primary cured film according to any one of claims 1 to 3, wherein, The thickness of the primary cured film is greater than 0.2µm and less than 500µm.

12. A secondary curing film, which is formed by further heating and curing the primary curing film according to any one of claims 1 to 11.

13. A film laminate comprising at least two layers selected from the group consisting of a substrate layer, a decorative layer, and an adhesive layer, wherein at least one layer constituting the film laminate comprises a primary cured film according to any one of claims 1 to 11, or a secondary cured film according to claim 12.

14. A method for manufacturing a secondary curing film, comprising: The process of attaching the one-cured film according to any one of claims 1 to 11 to the molded body while heating it at a temperature of 50°C or higher and 140°C or lower in a manner that follows the molded body; The process involves heating the attached resin composition at a temperature above 50°C and below 180°C to cure it.

15. The method for manufacturing a secondary cured film according to claim 14, wherein, The ratio γ / γ´ of the number of moles of functional group X contained in the primary cured film to the number of moles of functional group X contained in the secondary cured film is 0.1 or more and 0.9 or less.

16. The method for manufacturing a secondary cured film according to claim 14 or 15, wherein, The number of moles γ of functional group X contained in 1 kg of the primary cured film is 0.05 or more and 1.0 or less, and The number of moles γ' of functional group X contained in 1 kg of the secondary cured film is 0.5 or more and 10 or less.

17. A method of using a one-time cured film, comprising: The process of attaching the one-cured film according to any one of claims 1 to 11 to the molded body while heating it at a temperature of 50°C or higher and 140°C or lower in a manner that follows the molded body; The process of curing the attached resin composition by heating it at a temperature above 50°C and below 180°C.

18. An article protected by a primary cured film according to any one of claims 1 to 11, a secondary cured film according to claim 12, or a film laminate according to claim 13.

19. An article protected by a secondary cured film obtained by the manufacturing method of claim 14.

Images