Photocurable material, photocurable film, and cured product
Patent Information
- Application Number
- JP2024503757
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Filing Date
- 2024-01-19
- Publication Date
- 2025-09-30
Abstract
Description
Photocurable material, photocurable film, and cured product
[0001] The present invention relates to a photocurable material. The present invention also relates to a photocurable film made using the photocurable material, and a cured product of the photocurable material.
[0002] Imide compounds have excellent heat resistance and flame retardancy and are therefore widely used in applications such as automotive applications and electronic components. For example, Patent Document 1 discloses a polyimide derived from a specific aromatic diamine compound and a specific aromatic tetracarboxylic dianhydride as a polyimide used in a heat-resistant film. Imide compounds are also often used in photocurable materials. For example, Patent Document 2 discloses a photosensitive resin composition containing a specific polyimide precursor, a (meth)acrylic compound, a photoinitiator, and the like.
[0003] JP 2015-7219 A JP 2006-342310 A
[0004] Conventionally, imide compounds and maleimide compounds have high heat resistance, but have problems with mechanical strength such as toughness, and are therefore often used in combination with (meth)acrylic compounds and catalytic components such as photopolymerization initiators, photopolymerization catalysts, thermal polymerization initiators, and curing accelerators, as in the photosensitive resin composition disclosed in Patent Document 2. Therefore, the inclusion of these components has caused problems such as reduced heat resistance, outgassing, and the resulting odor and toxicity.
[0005] An object of the present invention is to provide a photocurable material that has excellent heat resistance, mechanical strength, and low outgassing. Another object of the present invention is to provide a photocurable film using the photocurable material, and a cured product of the photocurable material.
[0006] Disclosure 1 provides a photocurable material containing an imide compound, the imide compound comprising an imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond, the imide compound either not containing a (meth)acrylic compound, or the content of the (meth)acrylic compound relative to 100 parts by mass of all imide compounds comprising the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond is less than 1 part by mass, and the imide compound either not containing a catalyst component, or the content of the catalyst component relative to 100 parts by mass of all imide compounds comprising the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond is less than 0.1 parts by mass, and the photocurable material is irradiated with ultraviolet light having a wavelength of 365 nm equivalent to 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The photocurable material is a photocurable material in which a gel fraction of a cured product obtained by irradiating the photocurable material is 80 mass% or more. Disclosure 2 is the photocurable material of Disclosure 1, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from a dimer diamine having a polymerizable carbon-carbon double bond. Disclosure 3 is the photocurable material of Disclosure 1 or 2, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from a dimer diamine and a compound having a structure derived from a trimer triamine. Disclosure 4 is the photocurable material of Disclosure 1, 2, or 3, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a maleimide group in the entire imide compound. Disclosure 5 is the photocurable material of Disclosure 1, 2, 3, or 4, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a maleimide group and a compound not having a maleimide group in the entire imide compound. Disclosure 6 is the photocurable material of Disclosures 1, 2, 3, 4, or 5, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from an aromatic acid anhydride. Disclosure 7 is the photocurable material of Disclosures 1, 2, 3, 4, or 5, wherein the photocurable material is irradiated with ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２The photocurable material of Disclosure 1, 2, 3, 4, 5, or 6 is a photocurable material obtained by irradiation with light, wherein the 1% weight loss temperature of the cured product obtained by irradiation is 300°C or higher. Disclosure 8 is a photocurable film obtained by using the photocurable material of Disclosure 1, 2, 3, 4, 5, 6, or 7. Disclosure 9 is a cured product of the photocurable material of Disclosure 1, 2, 3, 4, 5, 6, or 7. The present invention is described in detail below.
[0007] The present inventors have considered that by using an imide compound having a specific structure, it would be possible to easily adjust the gel fraction of a photocured product to a specific value or more, thereby providing sufficient curability, without using a (meth)acrylic compound or a catalyst component. As a result, they have found that a photocurable material having excellent heat resistance, mechanical strength, and low outgassing can be obtained, and have completed the present invention.
[0008] The photocurable material of the present invention contains an imide compound. The imide compound includes an imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond (hereinafter also referred to as the "imide compound of the present invention"). By containing the imide compound of the present invention, the photocurable material of the present invention does not contain a (meth)acrylic compound or a catalyst component, and the gel fraction of the product cured by light irradiation is set to 80 mass% or more, thereby achieving excellent heat resistance and low outgassing.
[0009] The imide compound according to the present invention has a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond. Because the imide compound according to the present invention has a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond, the gel fraction of the cured product of the obtained photocurable material can be easily adjusted to the range described below, and the cured product also has excellent heat resistance. In this specification, the term "polymerizable carbon-carbon double bond" does not include carbon-carbon double bonds that constitute aromatic rings.
[0010] The preferred lower limit of the number of polymerizable carbon-carbon double bonds contained in one molecule of the imide compound according to the present invention is 1. When the number of polymerizable carbon-carbon double bonds is 1 or more, the resulting photocurable material has better curability and heat resistance. The more preferred lower limit of the number of polymerizable carbon-carbon double bonds is 2. There is no particular preferred upper limit of the number of polymerizable carbon-carbon double bonds, but the substantial upper limit is 10.
[0011] Examples of the aliphatic amine having a polymerizable carbon-carbon double bond include aliphatic diamines derived from dimer acids, linear or branched aliphatic diamines, aliphatic ether diamines, aliphatic alicyclic diamines, aliphatic triamines derived from trimer acids, and linear or branched aliphatic triamines, all of which are amine compounds having a polymerizable carbon-carbon double bond in their skeletons. Examples of the aliphatic diamines derived from dimer acids include non-hydrogenated dimer diamines and partially hydrogenated dimer diamines. Among these, dimer diamines having a polymerizable carbon-carbon double bond are preferred because they facilitate the adjustment of the gel fraction of the resulting cured photocurable material to the range described below. Non-hydrogenated or partially hydrogenated dimer diamines having a polymerizable carbon-carbon double bond are more preferred because they result in the resulting cured photocurable material having superior curability and heat resistance. That is, the imide compound according to the present invention preferably contains a compound having a structure derived from a dimer diamine having a polymerizable carbon-carbon double bond.
[0012] Furthermore, as the aliphatic amine having a polymerizable carbon-carbon double bond, a mixture of dimer diamine and trimer triamine is also preferred, since this makes it easier to adjust the gel fraction of the resulting cured product of the photocurable material to the range described below. That is, the imide compound according to the present invention also preferably contains a compound having a structure derived from dimer diamine and a compound having a structure derived from trimer triamine. The ratio of dimer diamine to trimer triamine in the mixture of dimer diamine and trimer triamine (dimer diamine / trimer triamine) is preferably in the range of 98 / 2 to 70 / 30 (mass ratio), more preferably 95 / 5 to 80 / 20 (mass ratio). By setting the ratio of dimer diamine to trimer triamine within the above range, a cured product with superior heat resistance and mechanical strength can be obtained.
[0013] The structure derived from the dimer diamine is preferably at least one structure selected from the group consisting of a structure represented by the following formula (1-1), a structure represented by the following formula (1-2), a structure represented by the following formula (1-3), and a structure represented by the following formula (1-4). Among these, the structure represented by the following formula (1-2) is more preferred.
[0014]
[0015] In formulas (1-1) to (1-4), R １ ~R １６ are each independently a linear or branched hydrocarbon group, and * represents a bond. In the imide compound according to the present invention, the bond * is bonded to N of the imide group.
[0016] In the above formulas (1-1) to (1-4), R １ ~R １６ The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ , R ９ and R１０ , R １１ and R １２ , R １３ and R １４ , and R １５ and R １６ The total number of carbon atoms (hereinafter simply referred to as "total number of carbon atoms") is preferably 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the resulting cured product of the photocurable material will have better flexibility and mechanical strength. The total number of carbon atoms is more preferably 9 or more, even more preferably 12 or more, and even more preferably 14 or more. Furthermore, the total number of carbon atoms is more preferably 35 or less, even more preferably 25 or less, and even more preferably 18 or less.
[0017] In the group represented by the formula (1-1), the group represented by the formula (1-2), the group represented by the formula (1-3), and the group represented by the formula (1-4), the optical isomerism is not particularly limited, and any optical isomerism is included.
[0018] The photocurable material of the present invention preferably contains a compound having a maleimide group in the entire imide compound including the imide compound of the present invention (hereinafter simply referred to as "entire imide compounds"). By containing the compound having a maleimide group, the gel fraction of the cured product of the photocurable material obtained can be easily adjusted to the range described below, and the cured product also has excellent heat resistance and low outgassing properties. The photocurable material of the present invention more preferably contains the compound having a maleimide group as the imide compound of the present invention.
[0019] When the photocurable material of the present invention contains the compound having a maleimide group, the photocurable material of the present invention may contain only the compound having a maleimide group within the entire imide compound, or may contain both the compound having a maleimide group and a compound not having a maleimide group. When the photocurable material of the present invention contains both the compound having a maleimide group and the compound not having a maleimide group within the entire imide compound, the content of the compound having a maleimide group per 100 parts by mass of the entire imide compound is preferably 20 parts by mass or more, and preferably 90 parts by mass or more. When the content of the compound having a maleimide group is 20 parts by mass or more, the gel fraction of the cured product of the photocurable material obtained can be easily adjusted within the range described below, and the heat resistance is also superior. When the content of the compound having a maleimide group is 90 parts by mass or less, the mechanical strength of the cured product of the photocurable material obtained is superior. The lower limit of the content of the compound having a maleimide group is more preferably 30 parts by mass, and the upper limit is more preferably 80 parts by mass.
[0020] The imide compound according to the present invention preferably contains a compound having a structure derived from an aromatic acid anhydride, which allows the obtained cured product of the photocurable material to have better heat resistance.
[0021] Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyrimidinyl ether ... benzenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyl)ethane bis(diphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyridine Examples of the anhydrides include thiophene-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid). Of these, 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid) anhydride is preferred.
[0022] The weight-average molecular weight of the imide compound according to the present invention is preferably 600 in lower limit and 50,000 in upper limit. When the weight-average molecular weight of the imide compound according to the present invention is 600 or more, the cured product of the obtained photocurable material has excellent low outgassing properties. When the weight-average molecular weight of the imide compound according to the present invention is 50,000 or less, the obtained photocurable material has excellent coatability and film-forming properties. The weight-average molecular weight of the imide compound according to the present invention is more preferably 1,000 in lower limit and 30,000 in upper limit. In this specification, the "weight-average molecular weight" is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, for example, it can be measured using an Acquity APC system (manufactured by Waters Corporation) under the following conditions: a mobile phase of THF, a flow rate of 1.0 mL / min, a column temperature of 40°C, a sample concentration of 0.2 mol%, and an RI-PDA detector. The column may be, for example, HR-MB-M 6.0×150 mm (manufactured by Waters Corporation).
[0023] Specific examples of the imide compound according to the present invention include compounds having a structural unit represented by the following formula (2) and having a polymerizable carbon-carbon double bond in the structural unit represented by formula (2) or outside the structural unit represented by formula (2).
[0024]
[0025] In formula (2), P １ represents an aromatic acid anhydride residue, and Q １ represents an aliphatic amine residue.
[0026] Above P １ Examples of aromatic acid anhydrides from which the acid dianhydride residue represented by the formula (I) is derived include the aromatic acid anhydrides described above.
[0027] The above Q １ Examples of the aliphatic amine from which the aliphatic amine residue represented by the formula (I) is derived include the above-mentioned aliphatic amines having a polymerizable carbon-carbon double bond.
[0028] Examples of methods for producing the imide compound of the present invention include a method of reacting the aliphatic amine having a polymerizable carbon-carbon double bond with the aromatic acid anhydride. Alternatively, the compound having the maleimide group can be obtained as the imide compound of the present invention by reacting the aliphatic amine having a polymerizable carbon-carbon double bond with the aromatic acid anhydride and then further reacting the resulting mixture with maleic anhydride or the like.
[0029] The photocurable material of the present invention does not contain a (meth)acrylic compound, or the content of the (meth)acrylic compound is less than 1 part by mass relative to 100 parts by mass of the total imide compounds. By not containing the (meth)acrylic compound, or by containing the (meth)acrylic compound in an amount of less than 1 part by mass relative to 100 parts by mass of the total imide compounds, the photocurable material of the present invention exhibits excellent heat resistance, mechanical strength, and low outgassing. The content of the (meth)acrylic compound is preferably less than 0.5 parts by mass, and most preferably 0 parts by mass, i.e., the photocurable material of the present invention does not contain the (meth)acrylic compound. In this specification, the term "(meth)acrylic" refers to acrylic or methacrylic, the term "(meth)acrylic compound" refers to a compound having a (meth)acryloyl group, and the term "(meth)acryloyl" refers to acryloyl or methacryloyl.
[0030] The photocurable material of the present invention does not contain a catalyst component, or the content of the catalyst component is less than 0.1 parts by mass relative to 100 parts by mass of the imide compound. The catalyst component refers to a photopolymerization initiator, photopolymerization catalyst, thermal polymerization initiator, curing accelerator, etc. By not containing the catalyst component or by having the catalyst component content less than 0.1 parts by mass, the photocurable material of the present invention exhibits excellent low outgassing properties. Furthermore, by not containing the catalyst component or by having the catalyst component content less than 0.1 parts by mass relative to 100 parts by mass of the imide compound, a cycloalkane skeleton is more easily formed by a cyclization reaction between polymerizable carbon-carbon double bonds during photocuring, thereby producing a cured product with excellent heat resistance and mechanical strength. Furthermore, while typical photo- or thermal radical curing systems are susceptible to oxygen inhibition and may suffer from poor curing in the atmosphere, resulting in reduced heat resistance, by not containing the above catalyst component or by containing less than 0.1 parts by mass of the catalyst component, the cyclization reaction in a non-radical system is facilitated, and a cured product with excellent heat resistance and mechanical strength can be obtained. The content of the above catalyst component is preferably less than 0.05 parts by mass, and most preferably 0 parts by mass, i.e., the photo-curable material of the present invention does not contain the above catalyst component.
[0031] The photocurable material of the present invention may contain other components in addition to the imide compound of the present invention, as long as they are other than the catalyst component and the (meth)acrylic compound in amounts exceeding the above-mentioned amounts, but the photocurable material of the present invention may consist solely of the imide compound of the present invention. When the photocurable material of the present invention contains the other components, the lower limit of the content of the imide compound of the present invention per 100 parts by mass of the photocurable material of the present invention is preferably 50 parts by mass, and more preferably 70 parts by mass.
[0032] Examples of the other components include inorganic fillers, organic fillers, epoxy resins, phenoxy resins, phenolic resins, cyanate resins, polyimide resins, benzoxazine resins, leveling agents, flame retardants, coupling agents, colorants, antioxidants, ultraviolet absorbers, antifoaming agents, thickeners, and thixotropy-imparting agents.
[0033] When the photocurable material of the present invention contains the other components, the photocurable material of the present invention can be produced, for example, by mixing the imide compound of the present invention with the other components using a mixer, such as a homodisper, a universal mixer, a Banbury mixer, or a kneader.
[0034] The photocurable material of the present invention is exposed to ultraviolet light of 365 nm wavelength equivalent at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The lower limit of the gel fraction of the cured product obtained by irradiation is 80% by mass. When the gel fraction of the cured product is 80% by mass or more, the photocurable material of the present invention can easily obtain a cured product with excellent heat resistance and low outgassing properties by light irradiation. The lower limit of the gel fraction of the cured product is preferably 85% by mass, and more preferably 90% by mass. There is no particular preferred upper limit of the gel fraction of the cured product, but the substantial upper limit is 100% by mass. In this specification, the irradiation amount of the "ultraviolet rays converted to a wavelength of 365 nm" means the irradiation amount calculated from the illuminance measured at a wavelength of 365 nm. The gel fraction of the cured product can be determined by irradiating ultraviolet rays converted to a wavelength of 365 nm with an ultra-high pressure mercury lamp at 30,000 mJ / cm. ２ After the photocurable material is cured by irradiating it with ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm, the curing strength is measured by the following method. ２ The cured product of the photocurable material obtained by irradiation is cut into a 50 mm x 100 mm flat rectangular shape to prepare a test piece. The obtained test piece is immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The mass of the dried test piece is measured, and the gel fraction is calculated using the following formula: Gel fraction (mass%) = 100 x (W ２ -W ０ ) / (W １ -W ０ ) (W ０ : Mass of the substrate, W １ : mass of test piece before immersion, W ２ : Mass of test piece after immersion and drying)
[0035] The photocurable material of the present invention is exposed to ultraviolet light of 365 nm wavelength equivalent at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The preferred lower limit of the 1% weight loss temperature of the cured product obtained by irradiation is 300°C. Since the 1% weight loss temperature of the cured product is 300°C or higher, the photocurable material of the present invention can be suitably used in applications requiring low outgassing and heat resistance. A more preferred lower limit of the 1% weight loss temperature of the cured product is 320°C. There is no preferred upper limit of the 1% weight loss temperature of the cured product, but the practical upper limit is 450°C. The 1% weight loss temperature of the cured product can be determined by thermogravimetry using a thermogravimetry device, where the temperature is increased from 30°C to 500°C at a rate of 10°C / min. An example of the thermogravimetry device is the TG / DTA6200 (manufactured by Hitachi High-Tech Science Corporation). In addition, the cured product for measuring the 1% weight loss temperature of the cured product was prepared by coating a photocurable material onto a substrate film so that the thickness after drying was 100 μm, drying the material, and then irradiating the material with ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The resin is cured by irradiation.
[0036] The photocurable material of the present invention is exposed to ultraviolet light of 365 nm wavelength equivalent at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The preferred lower limit of the glass transition temperature of the cured product obtained by irradiation is 40°C. Since the glass transition temperature of the cured product is 40°C or higher, the photocurable material of the present invention can be suitably used in applications requiring heat resistance in particular. The more preferred lower limit of the glass transition temperature of the cured product is 45°C, and the even more preferred lower limit is 50°C. There is no particular preferred upper limit of the glass transition temperature of the cured product, but the substantial upper limit is 300°C. In this specification, the "glass transition temperature" refers to the temperature at which a maximum due to micro-Brownian motion appears among the maximums of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. The glass transition temperature can be measured by a conventionally known method using a dynamic viscoelasticity measurement device or the like.
[0037] A film of the photocurable material of the present invention can be obtained by coating the photocurable material of the present invention on a substrate film and drying it. A photocurable film made using the photocurable material of the present invention also constitutes one aspect of the present invention.
[0038] The photocurable material of the present invention can be cured by irradiation with light. A cured product of the photocurable material of the present invention also constitutes the present invention.
[0039] The method of light irradiation is not particularly limited, and examples thereof include a method of irradiating light using an ultraviolet irradiation device such as an ultra-high pressure mercury lamp, a metal halide lamp, or an LED.
[0040] The preferred lower limit of the light irradiation dose in the above light irradiation is 1000 mJ / cm ２ The light irradiation dose is 1000 mJ / cm ２ By setting the amount to the above, the photocurable material of the present invention can be sufficiently cured by light irradiation. A more preferable lower limit of the light irradiation amount in the above light irradiation is 3000 mJ / cm. ２ There is no particular upper limit to the amount of light irradiation, but from the viewpoint of production efficiency, etc., the practical upper limit is 50,000 mJ / cm. ２ is.
[0041] The photocurable material of the present invention has excellent heat resistance, mechanical strength, and low outgassing, and is free from odor and toxicity, and is therefore suitable for use in applications such as adhesives for electronic materials, temporary fixing materials, sealing materials, multilayer substrate materials, and photosensitive insulating materials.
[0042] According to the present invention, it is possible to provide a photocurable material having excellent heat resistance, mechanical strength, and low outgassing. Furthermore, according to the present invention, it is possible to provide a photocurable film using the photocurable material, and a cured product of the photocurable material.
[0043] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[0044] (Synthesis Example 1) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 53.2 g (0.1 mol) of a mixture of dimer diamine and trimer triamine having a polymerizable carbon-carbon double bond (manufactured by Croda, "Priamine 1073") and 52.0 g (0.1 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by SABIC, "BISDA-1000") were added in this order. The dimer diamine / trimer triamine ratio in Priamine 1073 was 95 / 5 (mass ratio). A Dean-Stark tube and a condenser were attached to the round-bottom flask, and the resulting mixture was refluxed for 2 hours and cooled to room temperature. 300 mL of toluene was added to the round-bottom flask, and the mixture was allowed to stand to separate into layers, and the impurity lower layer was removed. The resulting solution was filtered through a glass-fritted funnel packed with silica gel, and the solvent was removed under vacuum to obtain an imide mixture (imide compound A) containing an imide compound having a structural unit represented by the following formula (3). The weight-average molecular weight of the resulting imide compound A was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as the eluent and an HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) column, and was found to be 23,000.
[0045]
[0046] (Synthesis Example 2) 250 mL of toluene was added to a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 53.2 g (0.1 mol) of a mixture of dimer diamine and trimer triamine having a polymerizable carbon-carbon double bond (manufactured by Croda, "Priamine 1071") and 46.8 g (0.09 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by SABIC, "BISDA-1000") were added in this order. The dimer diamine / trimer triamine ratio in Priamine 1071 was 80 / 20 (mass ratio). A Dean-Stark trap and a condenser were attached to the round-bottom flask, and the resulting mixture was refluxed for 2 hours and cooled to room temperature. 12.8 g (0.13 mol) of maleic anhydride was added to the reaction mixture, followed by 5 g (0.05 mol) of methanesulfonic anhydride. The resulting mixture was refluxed for an additional 12 hours, cooled to room temperature, and 300 mL of toluene was added to the round-bottom flask. The mixture was allowed to stand for layer separation, and the lower layer, which was an impurity, was removed. The resulting solution was filtered through a glass-fritted funnel packed with silica gel, and the solvent was removed under vacuum to obtain an imide mixture (imide compound B) containing an imide compound represented by the following formula (4). The weight-average molecular weight of the resulting imide compound B was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as the eluent and an HR-MB-M 6.0 x 150 mm column (manufactured by Waters Corporation), and was found to be 24,000.
[0047]
[0048] In formula (4), n is the number of repetitions.
[0049] Synthesis Example 3 An imide mixture (imide compound C) containing the imide compound represented by formula (4) was obtained in the same manner as in Synthesis Example 2, except that 53.2 g (0.1 mol) of a mixture of dimer diamine and trimer triamine having a polymerizable carbon-carbon double bond (manufactured by Croda, "Priamine 1073") was used instead of Priamine 1071. The dimer diamine / trimer triamine ratio in Priamine 1073 was 95 / 5 (mass ratio). The weight average molecular weight of the obtained imide compound C was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters)) using THF as the eluent and an HR-MB-M 6.0 × 150 mm column (manufactured by Waters), and was found to be 25,000.
[0050] Synthesis Example 4 An imide mixture (imide compound D) containing an imide compound represented by the following formula (5) was obtained in the same manner as in Synthesis Example 2, except that 53.2 g (0.1 mol) of a mixture of hydrogenated dimer diamine and trimer triamine having no polymerizable carbon-carbon double bond ("Priamine 1075" manufactured by Croda) was used instead of Priamine 1071. The dimer diamine / trimer triamine ratio in Priamine 1075 was 98 / 2 (mass ratio). The weight average molecular weight of the obtained imide compound D was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters)) using THF as the eluent and an HR-MB-M 6.0 × 150 mm column (manufactured by Waters), and was found to be 27,000.
[0051]
[0052] In formula (5), n is the number of repetitions.
[0053] Synthesis Example 5 An imide compound (imide compound E) represented by the following formula (6) was obtained in the same manner as in Synthesis Example 2, except that 17.2 g (0.1 mol) of 1,10-decanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Priamine 1071. The weight-average molecular weight of the obtained imide compound E was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm column (manufactured by Waters Corporation), and was found to be 18,000.
[0054]
[0055] In formula (6), n is the number of repetitions.
[0056] (Examples 1 to 7, Comparative Examples 1 to 6) Each material listed in Table 1 was added to 150 mL of toluene, mixed, and coated onto the release-treated surface of a PET film (release PET film) that had been subjected to release treatment on one side as a substrate film so that the dry film thickness would be 100 μm. The coating solution was then dried by heating at 100° C. for 10 minutes, thereby obtaining a photocurable film with a release PET film.
[0057] (Gel Fraction of Cured Product) The release PET film was peeled off from the obtained photocurable film with the release PET film, and the film was exposed to ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The photocurable film was cured by irradiating the film with light. The obtained cured product was cut into a 50 mm x 100 mm flat rectangular shape to prepare a test piece. The obtained test piece was immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The mass of the dried test piece was measured, and the gel fraction was calculated using the following formula. The results are shown in Table 1. Gel fraction (mass%) = 100 x (W ２ -W ０ ) / (W １ -W ０ ) (W ０ : Mass of the substrate, W １ : mass of test piece before immersion, W ２ : Mass of test piece after immersion and drying)
[0058] <Evaluation> The photocurable films obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Table 1.
[0059] (Glass Transition Temperature (Heat Resistance) of Cured Product) The release PET film was peeled off from the obtained photocurable film with the release PET film, and the film was exposed to ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The photocurable film was cured by irradiating the film with light. Dynamic viscoelasticity measurements were performed on the resulting cured product using a dynamic viscoelasticity measuring device under conditions of a grip width of 24 mm, a heating rate of 10°C / min, and a frequency of 10 Hz in the range of 0°C to 250°C, and the temperature at which the loss tangent (tan δ) reached its maximum was determined as the glass transition temperature. A DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) was used as the dynamic viscoelasticity measuring device. Heat resistance was evaluated by assigning a "◎" when the glass transition temperature was 70°C or higher, a "○" when it was 50°C or higher but less than 70°C, a "△" when it was 40°C or higher but less than 50°C, and an "×" when it was lower than 40°C.
[0060] (1% Weight Loss Temperature of Cured Product (Low Outgassing)) The release PET film was peeled off from the obtained photocurable film with the release PET film, and ultraviolet light equivalent to a wavelength of 365 nm was irradiated at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The photocurable film was cured by irradiating the film with light. 10 mg of the resulting cured product was weighed into an aluminum pan. The aluminum pan was placed in a thermogravimetric and differential thermal analyzer ("STA7200" manufactured by Hitachi High-Tech Science Corporation) and heated from 25°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere. The temperature at which the weight of the cured product had decreased by 1% was measured. Low outgassing was evaluated by assigning a "◎" when the 1% weight loss temperature was 350°C or higher, a "○" when it was 330°C or higher but less than 350°C, a "△" when it was 300°C or higher but less than 330°C, and an "×" when it was less than 300°C.
[0061] (Stress at Break (Mechanical Strength) of Cured Product) The release PET film was peeled off from the obtained photocurable film with the release PET film, and the film was exposed to ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２The photocurable film was cured by irradiating the film with light. Test pieces measuring 100 mm x 10 mm were prepared from the resulting cured product, and the stress at break was measured using a tensile tester (manufactured by Orientec Co., Ltd., "Tensilon RTC-1310") at 23°C, a gauge length of 50 mm, and a tensile speed of 300 mm / min. Mechanical strength was evaluated by assigning a "◎" when the stress at break was 20 MPa or more, "◯" when it was 15 MPa or more but less than 20 MPa, "△" when it was 10 MPa or more but less than 15 MPa, and "×" when it was less than 10 MPa.
[0062]
[0063] According to the present invention, it is possible to provide a photocurable material having excellent heat resistance, mechanical strength, and low outgassing. Furthermore, according to the present invention, it is possible to provide a photocurable film using the photocurable material, and a cured product of the photocurable material.
Claims
1. A photocurable material containing an imide compound, the imide compound includes an imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond, The imide compound does not contain a (meth)acrylic compound, or the content of the (meth)acrylic compound is less than 1 part by mass relative to 100 parts by mass of all imide compounds including the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond, and the imide compound does not contain a catalyst component, or the content of the catalyst component is less than 0.1 parts by mass relative to 100 parts by mass of the total imide compounds including the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond, The photocurable material was irradiated with ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The gel fraction of the cured product obtained by irradiation is 80% by mass or more. A photocurable material characterized by:
2. 2. The photocurable material according to claim 1, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from a dimer diamine having a polymerizable carbon-carbon double bond.
3. 3. The photocurable material according to claim 1, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from a dimer triamine and a compound having a structure derived from a trimer triamine.
4. 3. The photocurable material according to claim 1, wherein the imide compound as a whole contains a compound having a maleimide group, the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond.
5. 3. The photocurable material according to claim 1, wherein the imide compound as a whole contains a compound having a maleimide group and a compound not having a maleimide group, the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond.
6. 3. The photocurable material according to claim 1, wherein the imide compound having a structure derived from an aliphatic amine having a polymerizable carbon-carbon double bond includes a compound having a structure derived from an aromatic acid anhydride.
7. The photocurable material was irradiated with ultraviolet light equivalent to a wavelength of 365 nm at 30,000 mJ / cm using an ultra-high pressure mercury lamp. ２ 3. The photocurable material according to claim 1, wherein the cured product obtained by irradiation has a 1% weight loss temperature of 300[deg.] C. or higher.
8. A photocurable film obtained by using the photocurable material according to claim 1 or 2.
9. A cured product of the photocurable material according to claim 1 or 2.