Method for producing compositions, resin compositions, and composites

Abstract

The present disclosure relates to a resin composition containing composite of phenoxy resin and a compound having a carboxy group and a disulfide bond and a photoradical generator; and to a method for producing a composite that synthesizes a composite of a phenoxy resin and a compound having a carboxy group and a disulfide bond in the presence of a condensing agent.

Description

Technical Field

[0001] The present disclosure relates to methods for manufacturing compositions, resin compositions, and composites.

Background Art

[0002] Photo-softenable compositions that soften upon light irradiation are used in various applications. For example, Patent Document 1 discloses an image forming apparatus including a recording member having a photo-softenable resin layer composed of a photo-softenable resin.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] A main object of the present disclosure is to provide a resin composition having high elasticity and capable of exhibiting adhesiveness upon light irradiation.

Means for Solving the Problems

[0005] One aspect of the present disclosure relates to a resin composition containing a composite of a compound having a carboxy group and a disulfide bond and a phenoxy resin, and a photo radical generator.

[0006] Another aspect of the present disclosure relates to a composition containing a compound having a carboxy group and a disulfide bond, a phenoxy resin, and a condensing agent.

[0007] Another aspect of the present disclosure relates to a method for manufacturing a composite, in which a compound having a carboxy group and a disulfide bond and a phenoxy resin are reacted in the presence of a condensing agent.

Effects of the Invention

[0008] This disclosure provides a resin composition that has high elasticity and can exhibit tackiness upon light irradiation. Furthermore, this disclosure provides a method for producing a composite that exhibits photosoftening properties. [Modes for carrying out the invention]

[0009] The embodiments of this disclosure are described below. However, this disclosure is not limited to the embodiments described below.

[0010] In this specification, "photosoftening" refers to properties such as a decrease in viscosity, a decrease in elastic modulus, an increase in loss tangent (tanδ), or a decrease in hardness upon light irradiation. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. In this specification, numerical ranges indicated using "~" indicate a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage may be replaced with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way.

[0011] In this specification, the content of each component in a composition means the total amount of any multiple substances present in the composition, unless otherwise specified. Exemplary materials may be used individually or in combination of two or more, unless otherwise specified. "A or B" means either A or B, or both. "(meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl."

[0012] The resin composition according to this embodiment contains a composite of a compound having a carboxyl group and a disulfide bond and a phenoxy resin, and a photoradical generator.

[0013] The composite according to this embodiment is a reaction product of a compound having a carboxyl group and a disulfide bond (hereinafter sometimes referred to as "component (A)") and a phenoxy resin (hereinafter sometimes referred to as "component (B)"). The carboxyl group of component (A) and the hydroxyl group of component (B) can react to form an ester bond.

[0014] The composite according to this embodiment is presumed to have a disulfide bond derived from component (A) and an ester bond formed by the reaction of component (A) and component (B). The resin composition according to this embodiment exhibits high elasticity due to the inclusion of such a composite, and when the resin composition is irradiated with light, the disulfide bond in the composite decomposes (cleaves), generating a thiyl radical. At this time, if a photoradical generator is present in the resin composition, the thiyl radical reacts with the photoradical generator, and the thiyl radical is capped by the photoradical generator. This is thought to be a mechanism in which the compound having the disulfide bond becomes lower molecular weight, and the viscosity of the resin composition decreases. Another possible mechanism is that a photo-induced radical caused by the photoradical generator directly reacts with the disulfide bond, leading to the formation of a photo-induced radical-thioether bond and the generation of a thiyl radical. The thiyl radical then reacts with another photo-induced radical, and the compound having the disulfide bond itself becomes lower molecular weight, thus reducing the viscosity of the resin composition. The inventors hypothesize that the viscosity of the resin composition decreases, resulting in tackiness at low temperatures.

[0015] The composite according to this embodiment can be synthesized using a composition containing a compound having a carboxyl group and a disulfide bond as component (A), a phenoxy resin as component (B), and a condensing agent (hereinafter sometimes referred to as "component (C)").

[0016] (A) Component: A compound having a carboxy group and a disulfide bond The (A) component is not particularly limited as long as it is a compound having a carboxy group and a disulfide bond. The carboxy group of the compound may be 2 or more from the viewpoint of further increasing the elastic modulus of the resin layer formed from the resin composition. Examples of the compound having a carboxy group and a disulfide bond include 3,3'-dithiodipropionic acid, 3-carboxypropyldisulfide, and dithiodiglycolic acid.

[0017] The molar ratio of the (A) component when synthesizing the composite may be 0.5 to 2 mol, 0.9 to 1.2 mol, 0.95 to 1.1 mol, or 1.0 mol with respect to 1 mol of the (B) component.

[0018] (B) Component: Phenoxy resin Examples of the phenoxy resin include a resin obtained by polyaddition of a bifunctional epoxy resin and a bifunctional phenol compound, and a resin obtained by reacting a bifunctional phenol and epihalohydrin until polymerization. The phenoxy resin may be used alone or in combination of two or more.

[0019] Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F copolymer type phenoxy resin, biphenyl S type phenoxy resin, brominated phenoxy resin, phosphorus-containing phenoxy resin, and fluorene type phenoxy resin.

[0020] Since the phenoxy resin has a hydroxy group, it can react with the carboxy group of the (A) component to form an ester bond. The phenoxy resin may have an epoxy group at the terminal. When the phenoxy resin has a hydroxy group and an epoxy group, the composite can further have a structure derived from the reaction between the carboxy group of the (A) component and the epoxy group of the (B) component.

[0021] The epoxy equivalent of the phenoxy resin may be 3,000 to 30,000, 8,000 to 25,000, or 10,000 to 17,000.

[0022] The weight average molecular weight (Mw) of the phenoxy resin may be 10,000 to 150,000, 20,000 to 80,000, 30,000 to 70,000, or 40,000 to 60,000. Mw means the value measured by gel permeation chromatography (GPC) and converted using a calibration curve with standard polystyrene.

[0023] Commercially available products can be used as the phenoxy resin. Examples of commercially available phenoxy resins include YP-50, YP-55, YP-70, YPB-40PXM40, YPS-007A30, FX-280S, FX-281S, FX-293, and ZX-1356-2 (manufactured by Nippon Steel Chemical & Material Co., Ltd., trade names); 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827, and YL7864 (manufactured by Mitsubishi Chemical Corporation, trade names).

[0024] (C) component: Condensing agent The condensing agent can promote the condensation reaction between the (A) component and the (B) component. As the (C) component, a condensing agent capable of forming an ester bond by a dehydration condensation reaction between a carboxylic acid and a hydroxyl group can be used. Examples of the condensing agent include carbodiimide-based condensing agents, imidazole-based condensing agents, phosphonium-based condensing agents, uronium-based condensing agents, triazine-based condensing agents, phosphoryl azide-based condensing agents, quinoline-based condensing agents, and carbonate ester-based condensing agents.

[0025] Examples of carbodiimide-based condensing agents include N,N'-diisopropylcarbodiimide (DIC), N,N'-di-(tert-butyl)carbodiimide, N,N'-dicyclohexylcarbodiimide (DCC), N-(tert-butyl)-N'-ethylcarbodiimide (BEC), N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide (CMC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCHCl).

[0026] Examples of imidazole-based condensing agents include 1,1'-carbonyldiimidazole (CDI) and 1,1'-carbonyldi(1,2,4-triazole) (CDT).

[0027] Examples of phosphonium-based condensing agents include 1H-benzotriazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), (7-azabenzotriazole-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyAOP), chlorotripyrrolidinophosphonium hexafluorophosphate (PyCloP), bromotris(dimethylamino)phosphonium hexafluorophosphate (Brop), 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazine-4(3H)-one (DEPBT), and (ethylcyano(hydroxyimino)acetato-O2)-tri-(1-pyrrolidinyl)phosphonium hexafluorophosphate (PyOxim).

[0028] Examples of uronium-based condensing agents include O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), O-(benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium hexafluorophosphate (HBPyU), O-(benzotriazol-1-yl)-N, N,N',N'-bis(pentamethylene)uronium hexafluorophosphate (HBPipU), O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HCTU), O-(3,4-dihydro-4-oxo-1,2,3-benzotriazine-3-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HDBTU), O-(2-oxo-1(2H)pyridyl)-N,N,N',N'-tetramethyluro Nium hexafluorophosphate (TPTU), O-((ethoxycarbonyl)cyanomethyleneamino)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HOTU), O-((ethoxycarbonyl)cyanomethyleneamino)-N,N,N',N'-tetramethyluronium tetrafluoroborate (TOTU), N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium hexafluorophosphate (HSTU), N,N,N',N'-tetramethyl-O Examples include -(N-succinimidyl)uronium tetrafluoroborate (TSTU), dipyrrolidino(N-succinimidyloxy)carbenium hexafluorophosphate (HSPyU), S-(1-oxide-2-pyridyl)-N,N,N',N'-tetramethylthiouronium tetrafluoroborate (TOTT), and {{[(1-cyano-2-ethoxy-2-oxoethylidene)amino]oxy}-4-morpholinomethylene}dimethylammonium hexafluorophosphate (COMU).

[0029] Examples of triazine-based condensing agents include 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholium chloride n-hydrate (DMT-MM).

[0030] Examples of phosphoryl azide-based condensing agents include diphenyl phosphoryl azide (DPPA). Examples of quinoline-based condensing agents include 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ). Examples of carbonate ester-based condensing agents include di-tert-butyl dicarbonate (Boc2O).

[0031] The composite according to this embodiment can be synthesized by a manufacturing method in which a compound having a carboxyl group and a disulfide bond, which is component (A), and a phenoxy resin, which is component (B), are reacted in the presence of a condensing agent, which is component (C).

[0032] Reaction aids may be used during the above reaction. Examples of reaction aids include 4-dimethylaminopyridine (DMAP), 1-hydroxybenzotriazole (HOBt), and N-hydroxysuccinimide (HOSu).

[0033] When synthesizing the complex, it is preferable to use a solvent to dissolve components (A) and (B). Examples of solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonate esters such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP). The solvent may be used alone or in combination of two or more.

[0034] The reaction temperature for synthesizing the complex may be between 0°C and 200°C, or between 25°C and 70°C. The reaction time can be adjusted according to the reaction temperature, and may be, for example, between 1 and 100 hours.

[0035] The molar ratio of component (C) when synthesizing the complex may be 1.0 to 3.0 moles, 1.9 to 2.2 moles, 1.95 to 2.1 moles, or 2.0 moles per mole of component (A).

[0036] (D) Component: Photoradical generator The resin composition according to this embodiment can be prepared by mixing the above-mentioned complex with the photoradical generator, which is component (D). Examples of photoradical generators include intramolecular cleavage type photoradical polymerization initiators and hydrogen abstraction type photoradical polymerization initiators. Examples of intramolecular cleavage type photoradical polymerization initiators include benzyl ketal-based photoradical polymerization initiators; α-hydroxyacetophenone-based photoradical polymerization initiators, benzoin-based photoradical polymerization initiators, aminoacetophenone-based photoradical polymerization initiators, oxime ketone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, titanocene-based photoradical polymerization initiators, thiobenzoic acid S-phenyl polymerization initiators, and their high molecular weight derivatives. Examples of hydrogen abstraction type photoradical polymerization initiators include benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, and anthraquinone-based photoradical polymerization initiators.

[0037] The content of component (D) may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, based on the total amount of the resin composition, from the viewpoint of increasing the cleavage of disulfide bonds, and may be 20% by mass or less, 10% by mass or less, 8% by mass or less, or 5% by mass or less, from the viewpoint of suppressing the deterioration of the properties of the cured product of the resin composition.

[0038] (Other ingredients) The resin composition according to this embodiment may further contain, as other components, thermosetting resins such as epoxy resins, adhesion enhancers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy imparters, flame retardants, mold release agents, surfactants, lubricants, antistatic agents, and other additives. Known components can be used for the other components.

[0039] The resin composition according to this embodiment has the property that, upon light irradiation, the disulfide bonds (-SS-) in the composite are cleaved, and the compounds having disulfide bonds become lower in molecular weight and soften. By irradiating a resin layer formed from such a resin composition with light, the resin layer can soften and exhibit tackiness.

[0040] The light used for irradiation may be appropriately selected depending on the type of photoradical generator, etc. The light used for irradiation may be ultraviolet light or visible light. The wavelength of the light used for irradiation may be 150 to 830 nm. The irradiation may be performed, for example, using a light irradiation device, with an irradiation dose of 100 mJ / cm². 2 This can be done under the above conditions. Note that irradiation dose refers to the product of illuminance and irradiation time (seconds).

[0041] The light source used for light irradiation is not particularly limited and includes, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, LED lamps, metal halide lamps, excimer lamps, xenon lamps, etc.

[0042] The resin composition according to this embodiment can bond various adherends at low temperatures. For example, by irradiating a resin layer formed using the resin composition according to this embodiment with light, the resin layer can be softened, and an adherend can be bonded to the softened resin layer. [Examples]

[0043] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0044] The following compounds were prepared. (A) Ingredients: 3,3'-Dithiodipropionic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (B1) Ingredients: Fluorene-type phenoxy resin (Mw: 44000, epoxy equivalent: 15000, manufactured by Nippon Steel Chemical & Material Co., Ltd., product name "FX-293") (B2) Ingredients: Copolymerized phenoxy resin of bisphenol A and bisphenol F (Mw: 55000, manufactured by Nippon Steel Chemical & Material Co., Ltd., product name "YP-70") (C) Ingredient: 1-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ) (D1) Ingredients: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins BV, trade name "Omnirad TPO") (D2) Ingredients: 2,2-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins BV, trade name "Omnirad 651") Other ingredients: 3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, product name "Celoxide 2021P")

[0045] [Example 1] 40 parts by mass of component (B1) and 60 parts by mass of methyl ethyl ketone (MEK) were mixed at 60°C for 24 hours, and 0.28 parts by mass of component (A) was added and mixed for a further 2 hours to obtain a MEK solution. 0.659 parts by mass of component (C) was added to the MEK solution to obtain a composition containing components (A), (B1), and (C).

[0046] After stirring the above composition at 25°C for 32 hours, 2.05 parts by mass of component (D1) were added and the mixture was stirred at 60°C to prepare a resin composition containing a composite, which is a reaction product of FX-293 and 3,3'-dithiodipropionic acid, and component (D1), Omirad TPO.

[0047] (Evaluation of photosoftening properties) Approximately 10 g of the resin composition was weighed into a petri dish and placed in a vacuum chamber. The pressure was reduced using a vacuum pump to evaporate the solvent. The pressure reduction was continued while monitoring the weight until more than 90% of the solvent had evaporated. The change in elastic modulus of the resin composition from which the solvent had evaporated was measured while irradiating it with UV light using a photorheometer (photorheometer: manufactured by T.A. Instruments Japan Co., Ltd., product name "Discovery HR-2"). The measurement conditions for the elastic modulus are shown below. UV wavelength: 405nm LED Irradiation: 100mW / cm 2 , 0.1 seconds=100mJ / cm 2 (1 shot every 10 seconds) Gap: 100 μm Frequency: 1Hz

[0048] The elastic modulus of the resin composition before UV irradiation was 380 Pa, while the modulus of UV irradiation was 100 mJ / cm². 2 The elastic modulus after irradiation is 204 Pa, and the irradiation rate is 500 mJ / cm². 2 The elastic modulus after irradiation decreased to 70 Pa. This confirmed that the resin composition softened due to light irradiation.

[0049] (Evaluation of adhesiveness) To 100 parts by mass of the resin composition, 25 parts by mass of celloxide 2021P was added, and then the mixture was applied to glass using a squeegee to form a coating. The coating was dried in a 60°C oven for 1 hour to produce a resin film (thickness: approximately 300 μm). A PET film (manufactured by Fujimori Kogyo Co., Ltd., product name "Film Vina") was placed on the resin film, and UV light was irradiated from above the PET film (5000 mJ / cm²). 2 When the adhesion between the UV-irradiated area and the unirradiated area was checked by touch, the UV-irradiated area exhibited adhesiveness.

[0050] [Example 2] 49.3 parts by mass of component (B2) and 49.3 parts by mass of MEK were mixed at 60°C for 24 hours, and 0.439 parts by mass of component (A) was added and mixed for a further 2 hours to obtain a MEK solution. 1.03 parts by mass of component (C) was added to the MEK solution to obtain a composition containing components (A), (B2), and (C).

[0051] After stirring the above composition at 25°C for 32 hours, 2.54 parts by mass of component (D1) were added and the mixture was stirred at 60°C to prepare a resin composition containing a composite, which is a reaction product of YP-70 and 3,3'-dithiodipropionic acid, and component (D1), Omirad TPO.

[0052] [Example 3] A resin composition containing a composite, which is a reaction product of YP-70 and 3,3'-dithiodipropionic acid, and Omirad TPO, which is component (D1), was prepared in the same manner as in Example 2, except that the amount of component (D1) added was changed to 5.08 parts by mass.

[0053] [Example 4] A resin composition containing a composite, which is a reaction product of YP-70 and 3,3'-dithiodipropionic acid, and Omirad 651, which is component (D2), was prepared in the same manner as in Example 2, except that component (D1) was changed to component (D2).

[0054] Using the same procedure as in Example 1, resin films were prepared using the resin compositions of Examples 2 to 4, and their tackiness was evaluated. Adhesion was observed in the UV-irradiated areas.

Claims

1. A composite of a compound having a carboxyl group and a disulfide bond and a phenoxy resin, A resin composition containing a photoradical generator.

2. The resin composition according to claim 1, wherein the phenoxy resin has a hydroxyl group and an epoxy group.

3. The resin composition according to claim 1 or 2, wherein the composite has a disulfide bond and an ester bond.

4. Compounds having a carboxyl group and a disulfide bond, Phenoxy resin and A composition containing a condensing agent, A composition in which the condensing agent is a carbodiimide-based condensing agent, an imidazole-based condensing agent, a phosphonium-based condensing agent, a uronium-based condensing agent, a triazine-based condensing agent, a phosphoryl azide-based condensing agent, a quinoline-based condensing agent, or a carbonate ester-based condensing agent.

5. The composition according to claim 4, wherein the phenoxy resin has a hydroxyl group and an epoxy group.

6. A method for producing a composite, comprising reacting a compound having a carboxyl group and a disulfide bond with a phenoxy resin in the presence of a condensing agent, A method for producing a composite, wherein the condensing agent is a carbodiimide-based condensing agent, an imidazole-based condensing agent, a phosphonium-based condensing agent, a uronium-based condensing agent, a triazine-based condensing agent, a phosphoryl azide-based condensing agent, a quinoline-based condensing agent, or a carbonate ester-based condensing agent.

7. The method for producing the composite according to claim 6, wherein the phenoxy resin has a hydroxyl group and an epoxy group.

8. The method for producing the composite according to claim 6 or 7, wherein the composite has a disulfide bond and an ester bond.