Visible or infrared laser curable cationic polymerization epoxy resin composition

Abstract

A visible or infrared laser curable resin composition that cures in a short time with low energy. provide. A visible or infrared laser curable cationic polymerization epoxy resin composition a cationically polymerizable epoxy resin composition comprising (A) an epoxy resin, and (B) an acid generator; .

Description

Technical Field

[0001] The present invention relates to a visible or infrared laser-curable cationic polymerization epoxy resin composition.

Background Art

[0002] Visible or infrared lasers can be intensively irradiated onto a targeted location, and thus are widely used in welding. For the same reason, visible or infrared lasers are also used for the purpose of curing thermosetting adhesives.

[0003] As a technique for curing a thermosetting adhesive with a visible or infrared laser, adhesives containing dicyandiamide or imidazole, as well as anionic polymerization adhesives, are widely used (Patent Document 1). However, these adhesives require high energy. For example, when using a heating oven, it is necessary to set the temperature to 150°C or higher. Such curing conditions are suitable for joining metals such as joining automotive body panels. However, they are not suitable for joining optical components such as assembling camera modules and electronic sensors. Due to the characteristics of these components themselves and the specifications of the finished products, it is not preferable to expose them to high temperatures. In addition, the optical components may be affected by high temperatures and shift from their predetermined positions. However, this should be avoided according to the specifications of the finished products.

[0004] Therefore, when joining a lens holder to a base holder in a camera module, a method is also used in which these are temporarily fixed by UV so that their positions do not shift, and then finally cured in a heating oven until the desired degree of curing is reached.

[0005] Also, adhesives containing dicyandiamide or imidazole, and anionic polymerization adhesives. In the case of visible or infrared laser-curable adhesives, in order to further accelerate curing, The addition of black pigment is primarily for the purpose of absorbing laser light and releasing thermal energy. This is widely practiced (Patent Documents 2 and 3). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent Application Publication No. US2017 / 0145268 [Patent Document 2] Japanese Patent Publication No. 2020-045435 [Patent Document 3] Japanese Patent Publication No. 2016-088980 [Overview of the project] [Problems that the invention aims to solve]

[0007] Adhesives containing dicyandiamide or imidazole, and anionic polymerization adhesives Therefore, pigments are added to facilitate curing, and these are visible or infrared laser-curable type conventional The inventors have found that conventional adhesives have the following problems. In conventional adhesives, only the area around the pigment becomes extremely hot, resulting in a deterioration of the physical properties of the cured product. This can lead to decomposition. In addition, only the surface where the pigment is present may harden, or excessive hardening may occur on the surface. There are also problems such as the absorbed energy becoming concentrated and causing burns.

[0008] This invention provides a visible or infrared laser that cures in a shorter time and with less energy compared to the conventional technology. The objective is to provide a laser-curable resin composition. [Means for solving the problem]

[0009] In order to solve the above problems, the inventors of the present invention conducted intensive studies and found that the above problems can be solved by a cationic polymerization type epoxy resin composition containing (A) an epoxy resin , and (B) an acid generator. The present invention was completed by further studies based on such findings and includes the following aspects.

[0010] Item 1. A visible or infrared laser-curable cationic polymerization type epoxy resin composition, comprising (A) an epoxy resin, and (B) an acid generator A cationic polymerization type epoxy resin composition. Item 2. The cationic polymerization type epoxy resin composition according to Item 1, wherein the epoxy resin (A) contains an alicyclic epoxy resin. Item 3. The cationic polymerization type epoxy resin composition according to Item 2, wherein the epoxy resin (A) further contains a glycidyl ether type epoxy resin. Item 4. The cationic polymerization type epoxy resin composition according to any one of Items 1 to 3, wherein the visible or infrared laser has a wavelength of 600 to 1200 nm. Item 5. Further comprising (C) an inorganic filler The cationic polymerization type epoxy resin composition according to any one of Items 1 to 4. Item 6. The cationic polymerization type epoxy resin composition according to any one of Items 1 to 5, wherein the acid generator is a photoacid generator or a thermal acid generator. Item 7. Selected from the group consisting of metal adhesion and the assembly of camera modules and electronic sensors A clicker used for at least one of the purposes described in any one of paragraphs 1 to 6. On-polymerization epoxy resin composition. Section 8. A cationic polymerization epoxy resin composition, (A) Epoxy resin, and (B) Acid generator including, Use of cationic polymerization epoxy resin compositions for visible or infrared laser curing. Section 9. A method for curing a cationic polymerization epoxy resin composition, By irradiating the aforementioned cationic polymerization epoxy resin composition with a visible or infrared laser, This includes a hardening process, The cationic polymerization epoxy resin composition is (A) Epoxy resin, and (B) Acid generator Methods that include... [Effects of the Invention]

[0011] By using the visible or infrared laser-curable resin composition of the present invention, compared to the conventional technology, Compared to other methods, it can be cured in a shorter time and with less energy. [Modes for carrying out the invention]

[0012] (A) epoxy resin The epoxy resin used in this invention may be any resin capable of cationic polymerization, and is not particularly limited. No. The reaction mechanism of cationic polymerization of epoxy resins is well known. Specifically, the present invention uses The epoxy resin can be any polymerization system in which the growth chain is a carbon cation (carbocation). The epoxy resin used in this invention reacts with the acid generated from the acid generator to form a carbocation. This generates a carbocation, and a growth reaction occurs between this carbocation and the epoxy resin used in this invention. And finally, a hardened product is obtained.

[0013] The epoxy resin used in this invention may be one type of epoxy resin, or as needed A combination of two or more epoxy resins is also acceptable.

[0014] The epoxy resin used in this invention includes alicyclic epoxy resins, which have excellent curing properties. Preferably, an alicyclic epoxy resin has an alicyclic ring within its molecule and forms the ring. This is an epoxy resin in which some of the carbon-carbon bonds are shared with the epoxy ring. As the phenyl resin, known types can be used.

[0015] The epoxy resin used in this invention, when it contains an alicyclic epoxy resin, has the following characteristics in terms of curability: Preferably 3% by weight or more, more preferably 5% by weight or more, relative to the total amount of xyline resin, Preferably contains 10% by weight or more of alicyclic epoxy resin.

[0016] The alicyclic epoxy resin used in this invention has an epoxy equivalent of, for example, 100 to 500, preferably More preferably, it is 100 to 400, and more preferably 100 to 300.

[0017] The alicyclic epoxy resin used in the present invention is not particularly limited, but for example, 3,4-E Poxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (dye) Cell Corporation's "Celoxide 2021P [CEL2021P]", ε-caprolactone modified 3' ,4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (Dye Cell Corporation's "Celoxide 2081 [CEL2081]", 1,2-epoxy-4-vinyl thucco Roxene (Daicel Corporation's "Celoxide 2000 [CEL2000]"), (Daicel (Shin-Etsu Chemical Co., Ltd.'s "Celoxide 8010 [CEL8010]"), (Shin-Etsu Chemical Co., Ltd.'s "KR-47") Examples include 0), etc.

[0018] The epoxy resin used in this invention is a glycidyl ether that imparts flexibility to the cured product. A small number of epoxy resins selected from the group consisting of epoxy resins and glycidyl ester type epoxy resins It is preferable that it contains at least one type of epoxy resin. These epoxy resins are alicyclic epoxy resins. Because the growth reaction is slower compared to xylene resin, the curing reaction persists even after laser irradiation. Furthermore, the molecular weight is only a few thousand. Therefore, it is possible to impart desirable flexibility to the final cured product. ru.

[0019] The glycidyl ether type epoxy resin and the glycidyl ester type epoxy resin used in the present invention The resin has an epoxy equivalent of, for example, 100 to 1000, preferably 100 to 800, more Preferably, it is between 100 and 600.

[0020] The glycidyl ether type epoxy resin and the glycidyl ester type epoxy resin used in the present invention The resin is preferably liquid or semi-solid at room temperature (approximately 23°C), but even if it is solid, it can dissolve. It can be used after being disassembled.

[0021] As for glycidyl ether type epoxy resins and glycidyl ester type epoxy resins, Preferably, it has an aromatic structure in the main chain. Glycidyl ether type epoxy resin, and Glycidyl ester type epoxy resins include polycyclic aromatic structures (naphthalene, anthracete). It may also have (for example, n) in its main chain.

[0022] In the epoxy resins mentioned above, which can be added to impart flexibility to the cured product, glycidyl Ether-type epoxy resins are preferred. Examples of glycidyl ether-type epoxy resins include Examples include bisphenol-type glycidyl ethers, etc.

[0023] As for bisphenol-type glycidyl ethers, bisphenol A type glycidyl ether bisphenol F type glycidyl ether, bisphenol AP type glycidyl ether bisphenol type B glycidyl ether, bisphenol type C glycidyl ether, bisphenol type B Sphenol E-type glycidyl ether and bisphenol G-type glycidyl ether, etc. It can be listed.

[0024] A preferred bisphenol A type glycidyl ether is (DIC Corporation's "EP ICLON 840), (DIC Corporation's "EPICLON 840S"), (DI (EPICLON 850 manufactured by C Corporation), (EPICLON 850 manufactured by DIC Corporation) 50S), (DIC Corporation's "EXA-850CRP"), (DIC Corporation's "E XA-850LC), (DIC Corporation's EXA-860), (DIC Corporation's "EXA-1050"), ("EXA-1055" manufactured by DIC Corporation), (Mitsubishi Chemical) (825) manufactured by Mitsubishi Chemical Corporation, (827) manufactured by Mitsubishi Chemical Corporation Company-made "828"), (Mitsubishi Chemical Corporation-made "1001"), (Mitsubishi Chemical Corporation Examples include the company's "1002" and Nippon Kayaku Co., Ltd.'s "RE-310S".

[0025] A preferred bisphenol F type glycidyl ether is (DIC Corporation's "EX A-830), (DIC Corporation's "EXA-830S"), (DIC Corporation's "E XA-835), (DIC Corporation's EXA-830CRP), (DIC Corporation) (Manufactured by EXA830LVP), (Manufactured by DIC Corporation EXA835LV), (Mitsubishi Chemical Corporation) (806 manufactured by CAL Corporation), (806H manufactured by Mitsubishi Chemical Corporation), (Mitsubishi Chemical Corporation) (Manufactured by Ru Co., Ltd. "807"), (Manufactured by Nippon Kayaku Co., Ltd. "RE-303SL"), and pheno As an example of an all-aralkyl epoxy, (Nippon Kayaku Co., Ltd.'s "NC3000L"), (Japan Examples include "NC2000L" manufactured by Kayaku Co., Ltd.

[0026] The epoxy resin used in this invention is a glycidyl ether type epoxy resin, or a glycidyl When an ester-type epoxy resin is included, the total epoxy resin provides flexibility to the cured product. For the body, glycidyl ether type epoxy resin and glycidyl ester type epoxy resin Fat is preferably 3% by weight or more, more preferably 5% by weight or more, and even more preferably Contains 10% or more by weight.

[0027] (B) Acidifying agent The acid generator used in this invention generates acid directly or indirectly using a visible or infrared laser. It is produced, and the acid reacts with epoxy resin (A) to generate a carbocation. It's fine if it's available, but it's not particularly limited.

[0028] In the above, as an acid generator that directly generates acid using a visible or infrared laser, Examples include photoacid generators. Photoacid generators generate acid when irradiated with light. It is a compound that produces acid. The photoacid generator has a part in its molecule that absorbs light and a part that is the source of acid. It has a cation part and an anion part. It is not particularly limited, but for example, an onion having a cation part and an anion part. Examples include onium salts. In these onium salts, the cation portion absorbs light in the portion where the cation is located. This applies, and the anionic portion becomes the source of acid.

[0029] The above onium salt has sulfonium ions, iodonium ions, as cation moieties. It contains phosphonium ions, quaternary ammonium ions, or diazonium ions, etc. It is also acceptable to use, for example, a triarylsulfonium ion as the sulfonium ion. It is possible to be there.

[0030] The above onium salt has PF6 as its anionic part. - SbF6 - BF4 - Having the above It's okay to be there.

[0031] As for photoacid generators, we have CPI-100P, CPI-101A, and CP manufactured by Sunapro Co., Ltd. I-200K, CPI-210S, CPI-310B, CPI-310FG, CPI-4 10S and IK-1; Irgacure 250, manufactured by Ciba Specialty Chemicals. Examples include the Irgacure 270 and the Elkem BLUESIL PI 2074. ru.

[0032] In the above, as an acid generator that indirectly generates acid using a visible or infrared laser, Examples include thermal acid generators. Thermal acid generators produce acid by absorbing heat. It is a compound. The heat generated by a visible or infrared laser causes the thermoacid generator to produce acid. If necessary, for example, inorganic fillers, etc., are appropriately added to the cation polymerization epoxy resin mixture of the present invention. By incorporating it into the product, it becomes easier to generate heat when irradiated with a visible or infrared laser. This makes it easier to generate acid from a comb or a heat-activated acid generator.

[0033] As a thermal acid generator, (King Industries' "TGA CXC1612", "T GA CXC1821), (Sanshin Chemical Industry Co., Ltd.'s "San-Aid SI-B2A"), (Sanshin Chemical Industry Co., Ltd. "San-Aid SI-B7"), (Sanshin Chemical Industry Co., Ltd. "Sa (Sun-Aid SI-B3A), (Sun-Aid SI-B3 manufactured by Sanshin Chemical Industry Co., Ltd.), ( Examples include "San-Aid SI-B5" manufactured by Sanshin Chemical Industry Co., Ltd.

[0034] The acid generator used in this invention may be one type of acid generator, or two or more types as needed. A combination of acid generators may also be used.

[0035] The cationic polymerization epoxy resin composition of the present invention, an acid generator, cationic polymerization epoxy For example, 0.01 to 10% by weight, preferably 0.1 to 8% by weight, relative to the total resin composition. It more preferably contains 0.1 to 5% by weight, and even more preferably 0.1 to 3% by weight.

[0036] (C) inorganic fillers The cationic polymerization epoxy resin composition of the present invention may further contain inorganic fillers. stomach.

[0037] The inorganic filler used in this invention may be one type of inorganic filler, or as needed A combination of two or more inorganic fillers is also acceptable.

[0038] Examples of inorganic fillers used in this invention include colloidal silica, hydrophobic silica, and fine Silica fillers such as fine silica and nanosilica, as well as acrylic beads, glass beads, etc. Examples include urethane beads, bentonite, acetylene black, and Ketjenblack. ru.

[0039] The inorganic filler used in this invention is defined as having a volume-average particle size (or, if not granular, its weight). The average maximum diameter is, for example, 0.01 to 50 μm, preferably 0.1 to 40 μm, more preferably In this specification, inorganic filler volume-average particles can be used. The diameter is specifically measured using a dynamic light scattering nanotrac particle size analyzer.

[0040] Commercially available inorganic fillers include high-purity synthetic spherical silica (Admatex "SO- E5'', average particle size: 2μm; ``SO-E2'', average particle size: 0.6μm), Silica (Co., Ltd. "FB7SDX" manufactured by Ryusen Co., Ltd. (average particle size: 10 μm), and silica (Micron Co., Ltd.) Examples include "TS-10-034P" (average particle size: 20 μm).

[0041] The cationic polymerization epoxy resin composition of the present invention, an inorganic filler, cationic polymerization epoxy For example, 40-80% by weight, preferably 50-70% by weight, relative to the total amount of the xyline resin composition. It contains.

[0042] (D) Other ingredients The cationic polymerization epoxy resin composition of the present invention further comprises, if necessary, one or more of the following: It may also contain other ingredients.

[0043] Other specific examples of components include oxetane resin. Epoxy resin compositions, in particular, in terms of imparting flexibility to the cured product, are glycidyl ether type epoxy resins. If it contains epoxy resin or glycidyl ester type epoxy resin, further oxet The presence of resin accelerates the curing of these epoxy resins by acid generators. Therefore, it is preferable.

[0044] The cationic polymerization epoxy resin composition of the present invention, oxetane resin, cationic polymerization epoxy The phenyl resin composition contains, for example, 3 to 60% by weight, preferably 5 to 50% by weight. It is.

[0045] Other ingredients include adhesive additives (e.g., silane) and coupling agents (titanium). Examples include phosphates and rheological modifiers (such as fumed silica).

[0046] Even if the cationic polymerization epoxy resin composition of the present invention does not contain a pigment The cationic polymerization system of the present invention can be efficiently cured with a visible or infrared laser. The phenyl resin composition may optionally contain a pigment.

[0047] Purpose The cationic polymerization epoxy resin composition of the present invention is cured with a visible or infrared laser. It can be used for the following purposes. In the present invention, the visible or infrared laser is specifically 6 This refers to materials having wavelengths of 00 to 1200 nm. The resulting product has a wavelength of preferably 800-1100 nm, more preferably 900-1100 nm. It can be used to harden with a laser.

[0048] The cationic polymerization epoxy resin composition of the present invention is preferably used in camera module assembly. It is used for the following purposes. More specifically, the cationic polymerization epoxy resin composition of the present invention Preferably, in the camera module assembly, the lens holder and the image sensor are fixed together. It is used to bond the substrate to the attached substrate. In the above, the camera module is particularly limited It is not specified, but is a small camera module used in smartphones, etc.

[0049] Furthermore, the cationic polymerization epoxy resin composition of the present invention is suitable for the assembly of electronic sensors. It can also be used in a suitable manner. [Examples]

[0050] By mixing each component in the composition ratio shown in Table 1 (the unit for each value in Table 1 is mg), Resin compositions for Examples 1 and 2, and Comparative Examples 1 to 4 were prepared, respectively. Specifically, each The ingredients are blended in any proportion, kneaded and dispersed using a three-roll mill, and then vacuum degassed. A resin composition was obtained.

[0051] The specific ingredients used are as follows: [Alicyclic epoxy resin] 3,4-Epoxycyclohexylmethyl-3',4'-Epoxycyclohexanecarboxylate (Daicel Corporation's "Celoxide 2021P [CEL2021P]") [Glycidyl ether] Bisphenol A type epoxy resin (DIC Corporation's "EPICLON 840") [Oxetane resin] 3-Ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane (Toagosei Co., Ltd.) (Manufactured by OXT 221) [Acid Generator] Thermal acid generator (King Industries "TGA CXC1821") [Filler] High-purity synthetic spherical silica (Admatex Co., Ltd. "SO-E5", average particle size: 2 μm) [Hardening agent 1] Latent polyamine-type curing agent (ADEKA "EH-5057P") [Hardening agent 2] Acid anhydride (MHAC-P, manufactured by Showa Denko Corporation) [Pigments] Carbon black (MA100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) [Acrylate resin] Bisphenol A diacrylate (SR-540, manufactured by Sartomer) [Peroxide] Organic peroxide, polymerization initiator ("Per Octa-O" manufactured by NOF Corporation)

[0052] The curing test was conducted as follows. The evaluation results are shown in Table 1. <Curing Test Method> Apply 0.01 cc of each epoxy resin composition to a glass slide and tilt it at a 90° angle. After irradiating with a 0nm laser using Panasonic Corporation's "CB1F," the appearance and touch The hardening properties of the bamboo skewers were evaluated during the examination.

[0053] [Table 1]

[0054] When the anionic epoxy resin composition of Comparative Example 1 was irradiated with a laser, it did not harden. Laser irradiation was performed on the anionic epoxy resin compositions of Comparative Examples 2 and 3, which contained carbon black. When this was done, carbonization or hardening was observed. When the acrylic resin composition of Comparative Example 4 was irradiated with a laser... In that case, it did not harden.

[0055] On the other hand, when the cationic epoxy resin composition of Example 1 was irradiated with a laser, it did not contain pigment. Despite this, hardening was observed after 5 seconds. The cationic epoxy resin composition of Example 1 Compared to the comparative resin composition without pigments, it cures in a shorter time and with less energy. This can be understood.

Claims

[Claim 1] A visible or infrared laser curable cationic polymerization type epoxy resin composition, (A) an epoxy resin including an alicyclic epoxy resin and a glycidyl ether epoxy resin; (B) an acid generator, (C) an oxetane resin, and (D) 40 to 80% by weight of an inorganic filler based on the total weight of the cationic polymerization epoxy resin composition - Including, A cationic polymerization type epoxy resin composition.