Composition, resin composition, and method for manufacturing composite

Abstract

This invention relates to a resin composition and a method for manufacturing a composite, wherein the resin composition comprises a composite of a compound having carboxyl groups and disulfide bonds and a phenoxy resin, and a photoinitiator. In the method for manufacturing the composite, the composite of the compound having carboxyl groups and disulfide bonds and the phenoxy resin is synthesized in the presence of a condensing agent.

Description

Technical Field

[0001] This invention relates to a composition, a resin composition, and a method for manufacturing a composite. Background Technology

[0002] Photosoftening compositions that soften upon light irradiation are used in various applications. For example, Patent Document 1 discloses an image forming apparatus comprising a recording component having a photosoftening resin layer made of a photosoftening resin.

[0003] Previous technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. Hei 11-190883 Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] The main objective of this invention is to provide a resin composition that has high elasticity and exhibits adhesive properties when exposed to light.

[0008] means for solving technical problems

[0009] One aspect of the present invention relates to a resin composition comprising: a complex of a compound having a carboxyl group and a disulfide bond and a phenoxy resin; and a photoradical initiator.

[0010] Another aspect of the present invention relates to a composition comprising: a compound having a carboxyl group and a disulfide bond, a phenoxy resin, and a condensing agent.

[0011] Another aspect of the present invention relates to a method for manufacturing a composite, wherein a compound having carboxyl groups and disulfide bonds is reacted with a phenoxy resin in the presence of a condensing agent.

[0012] Invention Effects

[0013] According to the present invention, a resin composition exhibiting high elasticity and adhesive properties upon light irradiation can be provided. Furthermore, according to the present invention, a method for manufacturing a composite exhibiting light-softening properties can be provided. Detailed Implementation

[0014] The embodiments of the present invention will now be described. However, the present invention is not limited to the following embodiments.

[0015] In this specification, "light softening property" refers to the property of exhibiting reduced viscosity, decreased elasticity, increased loss tangent (tanδ), and decreased hardness upon light irradiation. In this specification, the term "process" does not refer to an independent process; it is included in this terminology as long as the intended function of the process can be achieved, even when it cannot be clearly distinguished from other processes. In this specification, the numerical range indicated by "~" represents the range of values ​​recorded before and after "~", serving as both minimum and maximum values. In the numerical ranges described in stages in this specification, the upper or lower limit of a certain stage's numerical range can be replaced by the upper or lower limit of other stages' numerical ranges. In the numerical ranges described in this specification, the upper or lower limit of the numerical range can be replaced by the values ​​shown in the examples. Furthermore, the individually recorded upper and lower limits can be combined arbitrarily.

[0016] In this specification, the content of each component in the composition refers to the total amount of the various substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. Furthermore, unless otherwise stated, the illustrative materials may be used alone or in combination of two or more. "A or B" may include either A or B, or both. "(meth)acrylate" refers to at least one of acrylates and their corresponding methacrylates. The same applies to other similar expressions such as "(meth)acryloyl".

[0017] The resin composition involved in this embodiment contains a complex of a compound having a carboxyl group and a disulfide bond with a phenoxy resin and a photoradical initiator.

[0018] The complex involved in 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.

[0019] It is presumed that the composite involved in this embodiment has disulfide bonds originating from component (A) and ester bonds formed through the reaction of component (A) and component (B). The resin composition involved in this embodiment exhibits high elasticity by containing this composite. When the resin composition is irradiated with light, the disulfide bonds in the composite decompose (crack), generating sulfur free radicals. At this time, if a photoradical initiator is present in the resin composition, the sulfur free radicals react with the photoradical initiator, and the sulfur free radicals are capped by the photoradical initiator. Therefore, a mechanism can be considered where the molecular weight of the compound with disulfide bonds is reduced, thus decreasing the viscosity of the resin composition. Another mechanism can be considered where, as another mechanism, photoinduced free radicals induced by the photoradical initiator directly react with the disulfide bonds, causing the formation of photoinduced free radical-thioether bonds and the generation of sulfur free radicals. The sulfur free radicals then react with other photoinduced free radicals, causing the molecular weight of the compound with disulfide bonds to decrease, thus reducing the viscosity of the resin composition. The inventors presumably believe that by reducing the viscosity of the resin composition, adhesive properties at low temperatures are exhibited.

[0020] The composite described in 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)").

[0021] (A) Components: Compounds containing carboxyl groups and disulfide bonds.

[0022] (A) There are no particular limitations on the composition as long as it is a compound having a carboxyl group and a disulfide bond. From the viewpoint of further improving the elastic modulus of the resin layer formed from the resin composition, the compound may have two or more carboxyl groups. Examples of compounds having a carboxyl group and a disulfide bond include 3,3'-dithiodipropionic acid, 3-carboxypropyl disulfide, and dithiodiethylene glycol.

[0023] The molar ratio of component (A) to component (B) in the synthesis of the complex can be 0.5–2 moles, 0.9–1.2 moles, 0.95–1.1 moles, or 1.0 moles.

[0024] (B) Component: Phenoxy resin

[0025] Examples of phenoxy resins include resins obtained by addition polymerization of a difunctional epoxy resin with a difunctional phenolic compound, and resins obtained by reacting difunctional phenols with epoxy halides to polymerize them. A single phenoxy resin can be used alone, or in combination of two or more.

[0026] Examples of phenoxy resins include bisphenol A type phenoxy resins, bisphenol F type phenoxy resins, bisphenol A / bisphenol F copolymer phenoxy resins, biphenyl S type phenoxy resins, brominated phenoxy resins, phosphorus-containing phenoxy resins, and fluorene type phenoxy resins.

[0027] Phenoxy resins have hydroxyl groups, thus they can react with the carboxyl groups of component (A) to form ester bonds. Phenoxy resins may also have epoxy groups at the ends. When phenoxy resins have both hydroxyl and epoxy groups, the complex can also have a structure derived from the reaction between the carboxyl groups of component (A) and the epoxy groups of component (B).

[0028] The epoxy equivalent of phenoxy resins can be 3000–30000, 8000–25000, or 10000–17000.

[0029] The weight-average molecular weight (Mw) of phenoxy resins can be 10,000–150,000, 20,000–80,000, 30,000–70,000, or 40,000–60,000. Mw refers to the value determined by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0030] Phenoxy resins can be commercially available. 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., product names); 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827, and YL7864 (manufactured by Mitsubishi Chemical Corporation, product names).

[0031] (C) Ingredients: Condensing agent

[0032] A condensing agent can promote the condensation reaction between component (A) and component (B). As component (C), a condensing agent capable of forming an ester bond through the dehydration condensation reaction of a carboxylic acid and a hydroxyl group can be used. Examples of condensing agents include carbodiimide-based condensing agents, imidazole-based condensing agents, phosphonate-based condensing agents, urea-based condensing agents, triazine-based condensing agents, azidophosphate-based condensing agents, quinoline-based condensing agents, and carbonate-based condensing agents.

[0033] Examples of carbodiimide 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 ester)carbodiimide (CMC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl).

[0034] Examples of imidazole condensing agents include 1,1'-carbonyldiimidazole (CDI) and 1,1'-carbonylbis(1,2,4-triazole) (CDT).

[0035] Examples of phosphine-based condensing agents include 1H-benzotriazole-1-acyloxytris(dimethylamino)phosphine hexafluorophosphate (BOP), 1H-benzotriazole-1-acyloxytripyrrolidone phosphine hexafluorophosphate (PyBOP), (7-azabenzotriazole-1-acyloxy)tripyrrolidone phosphine hexafluorophosphate (PyAOP), chlorotripyrrolidone phosphine hexafluorophosphate (PyCloP), bromotris(dimethylamino)phosphine hexafluorophosphate (Brop), 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazine-4(3H)-one (DEPBT), and (ethylcyano((hydroxyimino)acetyl-O2)-tris-(1-pyrrolylalkyl)phosphine hexafluorophosphate (PyOxim).

[0036] Examples of urea-based condensing agents include o-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate (HBTU), o-(7-heterobenzotriazol-1-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate (HATU), o-(benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)urea hexafluorophosphate (HBPyU), and o-(benzotriazol-1-yl)-N,N ,N',N'-bis(pentamethylene)urea hexafluorophosphate (HBPipU), o-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate (HCTU), o-(3,4-dihydro-4-oxo-1,2,3-benzotriazine-3-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate (HDBTU), o-(2-oxo-1(2H)pyridine)-N,N,N',N' -Tetramethylurea hexafluorophosphate (TPTU), o-((ethoxycarbonyl)cyanimino)-N,N,N',N'-tetramethylurea hexafluorophosphate (HOTU), o-((ethoxycarbonyl)cyanimino)-N,N,N',N'-tetramethylurea tetrafluoroborate (TOTU), N,N,N',N'-tetramethyl-o-(N-succinimino)urea hexafluorophosphate (HSTU), N,N,N',N'-tetramethylurea tetrafluorophosphate The following are listed: β-o-(N-succinimide)urea tetrafluoroborate (TSTU), dipyrrolidone (N-succinimideoxy)carbomonium hexafluorophosphate (HSPyU), S-(1-oxo-2-pyridyl)-N,N,N',N'-tetramethylthiourea tetrafluoroborate (TOTT), and {{[(1-cyano-2-ethoxy-2-ethylene)amino]oxy}-4-morpholinomethylene}dimethylammonium hexafluorophosphate (COMU).

[0037] Examples of triazine condensing agents include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine chloride n-hydrate (DMT-MM).

[0038] Examples of azidophosphate condensing agents include diphenylazidophosphate (DPPA). Examples of quinoline condensing agents include 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ). Examples of carbonate condensing agents include di-tert-butyl dicarbonate (Boc2O).

[0039] The composite involved in this embodiment can be synthesized by a manufacturing method in the presence of a condensing agent as component (C) by reacting a compound having a carboxyl group and a disulfide bond as component (A) with a phenoxy resin as component (B).

[0040] When carrying out the above reaction, reaction auxiliaries can be used. Examples of reaction auxiliaries include 4-dimethylaminopyridine (DMAP), 1-hydroxybenzotriazole (HOBt), and N-hydroxysuccinimide (HOSu).

[0041] When synthesizing the complex, solvents used to dissolve components (A) and (B) are preferred. Examples of solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene, isopropylbenzene, and p-isopropyltoluene; aliphatic hydrocarbons such as hexane and heptane; cycloalkanes 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; carbonates such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP). One solvent may be used alone or in combination of two or more.

[0042] The reaction temperature for synthesizing the complex can range from 0℃ to 200℃, or from 25℃ to 70℃. The reaction time can be adjusted by the reaction temperature, for example, from 1 to 100 hours.

[0043] The molar ratio of component (C) to component (A) in the synthesis of the complex can be 1.0–3.0 mol, 1.9–2.2 mol, 1.95–2.1 mol, or 2.0 mol.

[0044] (D) Component: Photoradical initiator

[0045] By mixing the above-described composite with a photoradical initiator as component (D), the resin composition according to this embodiment can be prepared. Examples of photoradical initiators include intramolecular cracking photoradical polymerization initiators and hydrogen extraction photoradical polymerization initiators. Examples of intramolecular cracking 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-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, titanoceramic-based photoradical polymerization initiators, thiobenzoic acid S-phenyl polymerization initiators, and their high molecular weight derivatives. Examples of hydrogen extraction photoradical polymerization initiators include benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, and anthraquinone-based photoradical polymerization initiators.

[0046] Based on the total amount of the resin composition, from the viewpoint of increasing the cleavage of disulfide bonds, the content of component (D) can be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more. From the viewpoint of suppressing the reduction of the properties of the cured resin composition, it can be 20% by mass or less, 10% by mass or less, 8% by mass or less, or 5% by mass or less.

[0047] (Other ingredients)

[0048] The resin composition described in this embodiment may also 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, thixotropic agents, flame retardants, release agents, surfactants, lubricants, antistatic agents, and other additives. Other components can be well-known ingredients.

[0049] The resin composition described in this embodiment breaks the disulfide bonds (-SS-) in the composite by light irradiation. Compounds containing disulfide bonds have the property of softening by reducing their molecular weight. By irradiating a resin layer formed from this resin composition with light, the resin layer can be softened and exhibit adhesive properties.

[0050] The light used for irradiation can be appropriately selected based on the type of photoradical initiator. The light used for irradiation can be ultraviolet or visible light. The wavelength of the light used for irradiation can be 150–830 nm. For example, a light irradiation device can be used with an irradiation dose of 100 mJ / cm². 2 The above conditions must be met. Additionally, irradiance is the product of illuminance and irradiation time (in seconds).

[0051] There are no particular limitations on the light source used for illumination; examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, LED lamps, metal halide lamps, excimer lamps, and xenon lamps.

[0052] The resin composition according to this embodiment can bond various substrates at low temperatures. For example, a resin layer formed using the resin composition according to this embodiment can be irradiated with light to soften the resin layer, and the substrate can be bonded to the softened resin layer.

[0053] Example

[0054] The present invention will be described in more detail below with examples. However, the present invention is not limited to these examples.

[0055] The following compounds were prepared.

[0056] (A) Ingredients: 3,3'-Dithiodipropionic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0057] (B1) Composition: Fluorene-type phenoxy resin (Mw: 44000, epoxy equivalent: 15000, manufactured by NIPPON STEELC Chemical & Material Co., Ltd., product name "FX-293")

[0058] (B2) Composition: Bisphenol A and Bisphenol F copolymer phenoxy resin (Mw: 55000, manufactured by NIPPON STEELC Chemical & Material Co., Ltd., product name "YP-70")

[0059] (C) Ingredient: 1-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ)

[0060] (D1) Ingredients: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins BV, product name "Omnirad TPO")

[0061] (D2) Ingredients: 2,2-Dimethoxy-2-phenylacetophenone (manufactured by IGM Resins BV, product name "Omnirad 651")

[0062] Other ingredients: 3',4'-epoxycyclohexylmethyl, 3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation, product name "Celoxide 2021P")

[0063] [Example 1]

[0064] 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. Then, 0.28 parts by mass of component (A) were added, and the mixture was further mixed for 2 hours to obtain a MEK solution. 0.659 parts by mass of component (C) were added to the MEK solution to obtain a composition containing components (A), (B1), and (C).

[0065] After stirring the above composition at 25°C for 32 hours, 2.05 parts by weight of component (D1) were added and stirred at 60°C to prepare a resin composition containing a complex as a reactant of FX-293 and 3,3'-dithiodipropionic acid and Omirad TPO as component (D1).

[0066] (Evaluation of light softening properties)

[0067] Approximately 10 g of the resin composition was measured into a petri dish and placed in a vacuum pan. The vacuum was then reduced to allow the solvent to evaporate. The pressure was maintained until at least 90% of the solvent had evaporated, and the weight was measured simultaneously. The change in elastic modulus was determined while the solvent-evaporated resin composition was irradiated with UV light using an photorheometer (manufactured by TA Instruments Japan Inc., product name "Discovery HR-2"). The conditions for measuring the elastic modulus are shown below.

[0068] LED with UV wavelength: 405nm

[0069] Irradiation: 100mW / cm 2 0.1 seconds = 100 mJ / cm 2 (Once every 10 seconds)

[0070] Gap: 100μm

[0071] Frequency: 1Hz

[0072] Compared to the resin composition having an elastic modulus of 380 Pa before UV irradiation, irradiation with 100 mJ / cm 2 The elastic modulus after UV irradiation is 204 Pa, and the irradiation intensity is 500 mJ / cm. 2 The elastic modulus subsequently decreased to 70 Pa. This confirms that light irradiation softened the resin composition.

[0073] (Evaluation of adhesive properties)

[0074] A coating film was formed by adding 25 parts by weight of Celoxide 2021P to 100 parts by weight of a resin composition and then applying it to glass using a scraper. The coating film was dried in an oven at 60°C for 1 hour to produce a resin film (thickness: approximately 300 μm). A PET film (manufactured by FUJIMORI KOGYOCO.,LTD., product name "film binder") was then placed on the resin film, and UV radiation (5000 mJ / cm²) was applied to the PET film. 2 When the adhesion between the UV-irradiated and unirradiated areas is confirmed by touch, the UV-irradiated area shows adhesiveness.

[0075] [Example 2]

[0076] 49.3 parts by weight of component (B2) and 49.3 parts by weight of MEK were mixed at 60°C for 24 hours, and 0.439 parts by weight of component (A) were added. The mixture was then further mixed for 2 hours to obtain a MEK solution. 1.03 parts by weight of component (C) was added to the MEK solution to obtain a composition containing components (A), (B2) and (C).

[0077] After stirring the above composition at 25°C for 32 hours, 2.54 parts by weight of component (D1) were added and stirred at 60°C to prepare a resin composition containing a complex as a reactant of YP-70 and 3,3'-dithiodipropionic acid and Omirad TPO as component (D1).

[0078] [Example 3]

[0079] Except that the amount of component (D1) added was changed to 5.08 parts by weight, a resin composition comprising a complex as a reactant of YP-70 and 3,3'-dithiodipropionic acid and Omirad TPO as component (D1) was prepared in the same manner as in Example 2.

[0080] [Example 4]

[0081] Except for changing component (D1) to component (D2), a resin composition comprising a composite of YP-70 and 3,3'-dithiodipropionic acid as reactants and Omirad 651 as component (D2) was prepared in the same manner as in Example 2.

[0082] Using the same steps as in Example 1, and with the resin compositions of Examples 2-4, a resin film was prepared. When evaluating the adhesiveness, adhesiveness was observed in the UV-irradiated area.

Claims

1. A resin composition comprising: Complexes of compounds containing carboxyl groups and disulfide bonds with phenoxy resins; and Photoradix initiators, The phenoxy resin has hydroxyl and epoxy groups.

2. The resin composition according to claim 1, wherein, Based on the total amount of the resin composition, the content of the photoradical initiator is 0.1% by mass or more and 20% by mass or less.

3. The resin composition according to claim 1 or 2, wherein, The complex has disulfide bonds and ester bonds.

4. A composition comprising: Compounds containing carboxyl groups and disulfide bonds; Phenoxy resins containing hydroxyl and epoxy groups; and Condensing agent, The condensing agent is selected from at least one of the following groups: carbodiimide condensing agents, imidazole condensing agents, urea condensing agents, triazine condensing agents, azidophosphate condensing agents, quinoline condensing agents, and carbonate condensing agents.

5. The composition according to claim 4, wherein, The molar ratio of the compound having carboxyl groups and disulfide bonds is 0.5 to 2 moles relative to 1 mole of the phenoxy resin.

6. A method for manufacturing a composite, wherein, In the presence of a condensing agent, a compound containing carboxyl groups and disulfide bonds reacts with a phenoxy resin. The phenoxy resin has hydroxyl and epoxy groups.

7. The method for manufacturing the composite according to claim 6, wherein, The molar ratio of the compound having carboxyl groups and disulfide bonds is 0.5 to 2 moles relative to 1 mole of the phenoxy resin.

8. The method for manufacturing the composite according to claim 6 or 7, wherein, The complex has disulfide bonds and ester bonds.