TW530079B - Resin composition curable with actinic energy ray - Google Patents

Abstract

A resin composition curable with actinic energy rays which comprises (A) at least one resin curable with actinic energy rays and (B) a free-radical photopolymerization initiator. In a first embodiment of the composition, at least 50 wt.% of the component (A) is accounted for by (A') a resin curable with actinic energy rays which has one radical-polymerizable ethylenically unsaturated bond, one or more hydroxyl groups, and one or more aromatic rings per molecule. In a second embodiment, the component (A) is (A"") a resin curable with actinic energy rays which has one ethylenically unsaturated bond per molecule, and the composition further contains (C) an epoxy resin. The first embodiment also preferably contains (C) an epoxy resin. In a preferred embodiment, the composition further contains at least one member selected from the group consisting of (D) a saturated polyester resin, (E) a vinyltriazine derivative, and (F) a silane coupling agent. Such resin composition is useful as an adhesive or coating material of the actinic-energy-ray-curing type for use in the protection of various electrodes.

Description

530079 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) The technical field to which the invention pertains The present invention relates to activated energy ray-curable resin compositions, and in particular, to the protection of various electrodes such as copper and silver electrodes The electrode is a composition having a hardenable activation energy line. Prior art In general, various types of electrodes such as electronic components are known as protective agents (protective coatings) for external air (moisture) from thermosetting, ultraviolet curing, and room temperature curing resin compositions. For example, the thermosetting resin composition is an epoxy resin resin composition disclosed in Japanese Patent Publication No. 1-1 9 8 3 4 and the ultraviolet curing resin composition is Japanese Unexamined Patent Publication No. 6 0- The acrylic resin composition disclosed in Japanese Patent Publication No. 1 0 3 3 4. However, among these resin compositions, the thermosetting resin composition requires long-term heating during the hardening treatment, so the workability is poor, and there are concerns about Other materials cause adverse effects. Although the UV-curing resin composition has the advantages of fast curing speed and low-temperature curing, the curing shrinkage is large, so the adhesion of the cured material to the substrate is poor, the cured product remains skewed and cracks occur, and it has poor water resistance. Disadvantages. The room temperature curing resin composition does not require hardening equipment and has the advantage of being inexpensive. However, it takes a long time to harden, and it is necessary to ensure a hardening site, which has the disadvantage of poor workability. In contrast, the resin composition that can overcome the above-mentioned various shortcomings applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at the UV paper scale — — — — — — — — — — — i ^ wi --- ----- ^ -------- (Please read the precautions on the back before filling out this page) 530079 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) Wire hardening department Among resin compositions, a resin composition having a photocationic catalyst characterized by low hardening shrinkage has also been proposed (refer to Japanese Patent Publication No. 2-30326 and Japanese Patent Application Publication No. 5-186755). However, if such a resin composition is used on a metal electrode, a new problem that a metal electrode is easily corroded due to a photocation catalyst occurs. On the other hand, today's fine patterning of external electrodes, as represented by flat panel models, is based on the use of optical lithography to pattern the calcined silver paste on a glass substrate in a narrow pitch. Make it. Therefore, even if the metal electrode patterned in the narrow pitch is to be protected by the previous resin composition as described above, sufficient protection performance cannot be obtained. In addition, in order to reduce the thickness and thickness of electronic equipment, silver paste has been recently screen-printed on PET films to form electrodes (thin-film liquid crystals and touch panels). However, in addition to the so-called protection function, the protective film also has Important characteristics such as low bending, dimensional stability, and adhesion of film materials are required. Problems to be Solved by the Invention Therefore, the object of the present invention is to solve the problems of the prior art as described above, and to provide the advantages of maintaining the ultraviolet curing resin composition, water resistance, and excellent adhesion to the substrate, Active energy ray-curable resin composition capable of withstanding short circuit between electrodes caused by migration. Here, the performance that can withstand the short circuit between electrodes caused by migration is hereinafter referred to as "migration resistance". This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm), --------. 丨 丨 • -Packing --- (Please read the precautions on the back before filling this page) i > _ 530079 A7 B7 V. Description of the invention (5) (Please read the precautions on the back before filling out this page) In the formula, X is hydrogen atom or methyl group, Y is -C (CH3) 2-, S 〇2 —, CH2 — or a direct bond, R1 and R2 are linear, cyclic or branched alkyl groups having 1 to 12 carbon atoms, m is an integer of 0 to 4, and η is an integer of 0. An integer of ~ 5.尙 In the first aspect of the active energy ray-curable resin composition of the present invention, within a range that does not adversely affect the characteristics of the composition, (A 〃) can be compounded with two or more ethylenic compounds in the molecule. An activation energy ray-curable resin having a saturated double bond and / or an activation energy ray-curable compound other than the aforementioned (A /) component, such as an activation energy ray-curable resin having no hydroxyl group and an aromatic ring. This type of activation energy ray-curable resin (A 〃) is not particularly limited as long as it is a compound that makes the ethylenically unsaturated double bond undergo radical polymerization through irradiation with activation energy rays, but (meth) acrylic acid Esters are particularly preferred. Moreover, it may have a functional group other than acrylfluorenyl (methacrylfluorenyl). Furthermore, if it is monofunctional and has an aromatic ring and a cyclic ring in the resin skeleton, it is advantageous in terms of adhesion and water repellency. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs On the other hand, in the second aspect of the active energy ray-curable resin composition of the present invention, the active energy ray-curable resin (A) has an ethylenic property in the molecule. Unsaturated double-bond active energy ray hardening resin (A 必须) is an essential constituent, and it is characterized by being contained together with epoxy resin. This active energy ray hardening resin (A 〃) is to limit the number of official ken g groups involved in the reaction to one in one molecule, so that the effect of hardening shrinkage during photoradical polymerization is minimized, which helps prevent dense Decreased synergy. However, only with the above-mentioned activation energy ray hardening resin (A 〃), the migration resistance and the paper size apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 530079 A7 B7 V. Description of the invention () For Since the adhesiveness of the substrate is insufficient depending on the intended use, epoxy resin (C) must be used. Here, since epoxy resin (C) does not participate in hardening, it can effectively reduce hardening shrinkage (improve adhesion). The epoxy resin (C) is also effective in improving migration resistance, although the reason is unknown. The activation energy ray-curable resin (A 〃) is not particularly limited as long as it is a compound in which an ethylenically unsaturated double bond is radically polymerized by irradiation with g-rays through an activation chamber, but (meth) acrylic acid Esters are particularly preferred. Moreover, it may have a functional group other than acrylfluorenyl (methacrylfluorenyl). Furthermore, if an aromatic ring and a cyclic ring are contained in the resin skeleton, it is advantageous in terms of water repellency. Specific examples of such an active energy ray-curable resin (A 〃) include 4- (meth) acrylic fluorenyloxy tricyclo [5.2.1.1.〇2.6] decane, (meth) acrylic phenoxy Ethyl ester, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy poly (meth) acrylate Glycol ester, phenol E0 modified (meth) acrylate, p-cumylphenol E 0 modified (meth) acrylate, nonylphenol E 0 modified (meth) acrylate, nonylphenol P0 modified (meth) acrylate, 2-hydroxy-3 -phenoxypropyl acrylate, isobornyl (meth) acrylate, dicyclopentene acrylate (meth) acrylate, and dicyclo (meth) acrylate Monofunctional (meth) acrylates such as pentenoxyethyl ester, dicyclopentyl (meth) acrylate, etc. 0 These monofunctional (meth) acrylates can also be glycidyl (meth) Acrylate. Specifically, we can enumerate the size of ortho-biphenyl shrink paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------- · Packing --- (please first Read the notes on the back and fill in this page) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 530079 A7 B7 V. Invention Description (9), (C) Epoxy resin is an essential component, and it is also in the first aspect. With the addition of epoxy resin, improved properties can be achieved. As described above, since the epoxy resin (C) does not participate in the photo-hardening reaction, it can effectively reduce hardening shrinkage (improve adhesion). Epoxy resins (c) are well-known and commonly used epoxy resins, and examples thereof include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and brominated phenol A type. Epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol epoxy resin, bixylenol epoxy resin, alicyclic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin Glycidyl ether compounds such as epoxy resin, brominated phenol novolak lacquer type epoxy resin, bisphenol A novolac lacquer type epoxy resin, diglycidyl terephthalate, diglycidyl hexahydrophthalate , Glycidyl compounds such as diglycidyl dimer, triglycidyl isocyanurate, N, N'N /, N > -tetraglycidyl-m-xylylenediamine, N, N, N , N / -tetraglycidyl bisamine methylcyclohexane, N, N, glycidylamine compounds such as diglycidyl aniline and the like are known and commonly used epoxy compounds. These epoxy resins can be used alone or in combination of two or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -----------_- pack --- (Please read the precautions on the back before filling out this page) The active energy line hardening resin composition of the present invention Among these epoxy resins, it is particularly preferable to use an epoxy resin having a softening point of 40 ° C or more and a semi-solid or solid state at room temperature. Thereby, the surface hardenability (touch-drying property) and water resistance of a resin composition can be improved. Furthermore, by selecting an epoxy resin having a water-repellent skeleton, the water-repellency of the resin composition can be improved and migration can be effectively prevented. The inventors and others, from various water-repellent resins containing epoxy resin .. a H, 2 This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 530079 A7 B7 10 5. Description of the invention (), select the epoxy resin that is semi-solid or solid at room temperature as described above, as the resin that participates in migration resistance, and then Repeated review, it was found that among these epoxy resins, those having an allyl group epoxidized by peracetic acid have the following structure, that is, the molecule has a partial structure shown by the following general formula (3) An epoxy compound or an alicyclic epoxy compound having any one of the following formulae (4) or (5) has better migration resistance than derivatives of epichlorohydrin. Compared with epichlorohydrin derivatives, epoxy compounds with the following structure have excellent electrical characteristics because of the low ion concentration of impurities (please read the precautions on the back before filling this page).

tr- · · ~ · · · ⑷ ~ · · · (5) In the printed format of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, X is epoxy and / or vinyl, and p is 1 to 1 0 0 Integer. However, at least one epoxy group is contained in the molecule. In particular, the point of migration resistance is the ratio of the number of functional groups represented by the following formulae (a) and (b) in an epoxy compound having a partial structure represented by the following general formula (3) in the molecule (a ) / (b) is preferably on average 1 · 0 to 4 · 0. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 530079 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs B7____ 14 V. Description of the invention () A—189, A—1100, A—1120 And A — 1160, TSL — 8310 made by Toshiba Silicone Co., Ltd. — TSL — 8311, TSL — 8320, TSL — 8395, TSL — 8325, TSL — 8331, TSL — 8340, TSL — 8345, TSL — 8380, TSL — 8350, TSL — 8355, TSL — 8370, and TLS — 8375. In the activated-energy-ray-curable resin composition of the present invention described above, additives may be appropriately blended in addition to the aforementioned components. For example, organic or inorganic fillers can be blended from the viewpoints of reducing hardening shrinkage, reducing thermal expansion, improving dimensional stability, increasing elasticity, adjusting viscosity, improving thermal conductivity, increasing strength, and improving toughness. Polymers, ceramics, metals, metal oxides, metal salts, and the like can be used as such fillers. The shape may be particulate, fibrous, or the like, and is not particularly limited. That is, when blending the above polymers, it may be a polymer blend type or a polymer alloy type instead of a filling agent type, or it may be dissolved, semi-dissolved, or microdispersed in an active energy ray-curable resin composition. In addition, the active energy ray-curable resin composition of the present invention may be blended with colorants such as organic or inorganic pigments and dyes as additives, and used for coatings, inks, and the like. Furthermore, the active energy ray-curable resin composition of the present invention can be appropriately blended with a softener, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropic agent, and a dispersion stabilizer. Agent, fluidity 4 ^-(Please read the precautions on the back before filling this page) The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 530079 A7 B7 Appropriate organic solvents can be used, etc. Degree. Hereinafter, the present invention will be described in detail with examples and comparative examples, but the present invention is not limited to the following examples. The activated energy ray-curable resins (A-1) to (A-3) have the following chemical structures. V. Description of the invention (15) Additives as other additives The method of hardening the activation energy line of the present invention is coated on the substrate, and the wire is used to harden the ethylenically unsaturated bond. The light rays of the activation energy rays are pressure mercury lamps, ultra-high pressure mercury lamps, others, laser rays, and electron beams. Alas, the resin composition of the present invention is of any type. When used in a liquid state, the resin composition may be subjected to photoradical polymerization by irradiating the formed coating layer with activation energy, and low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure lamps, or metal halide lamps are suitable. It can also be used as an active energy material for exposure. Liquid, paste, and film can be used. In order to adjust the viscosity of the resin composition, a known viscosity adjuster can be used to adjust the viscosity. The following examples and comparative examples are read first. Notes for this page

This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 530079 A7 __B7 V. Description of the invention (16)

OH Examples 1 to 7 Each component shown in Tables 1 and 2 was mixed in a predetermined ratio with a stirring device to prepare an active energy ray-curable resin composition having various component compositions. Comparative Examples 1 to 6 Each component shown in Table 3 was mixed with a stirring device at a specified ratio to prepare an active energy ray-curable resin composition having various component compositions. ----------- Installation --- (Please read the notes on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Φ This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297 male f) 530079 A7 ___ B7 V. Description of invention (21) The time from the start to the short circuit. Printed (3) Adhesion test (for glass substrate) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: In the above migration resistance test (2), visually confirm the temperature of 85 ° C, relative humidity of 85%, DC Adhesion of glass and silver electrodes to paste after 1 500 hours at 1000 V. The evaluation was as follows. :: Even after 1500 hours or more, no floating or peeling was observed. 〇: After 15 hours, some floating was observed on the electrode. Δ: Peeled from the glass within 15 hours. X: Peel immediately after hardening. (4) Adhesion test (for PET film) For a resin film with a thickness of 1 〇 // // m thick, each resin composition is coated with a coater to a film thickness of 3 5 // m. After curing, A 2 cm x 5 cm film was cut out as a test piece. This was put in a constant temperature and humidity bath at a temperature of 40 ° C and a relative humidity of 95%, and the peeling state was evaluated. :: Floating and peeling did not occur even after 1000 hours or more. 〇: Floating and peeling did not occur until 1000 hours. Δ: Peeled at 1000 hours. X: Peeling occurs immediately after hardening or peeling occurs during test piece production (5) Bending measurement The amount of bending of the test piece produced by the aforementioned adhesion test (4) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- install— (Please read the precautions on the back before filling in this page) Order 530079 A7 B7 99 V. Description of the invention () 0 ◎: Bending amount is less than 1mm , Hardly bent. ○: The amount of bending is 2 mm or less. (Please read the precautions on the back before filling in this page) X: The bending amount is 2mm or more. (6) Restorability: A sample of each resin composition coated and hardened on a glass substrate in an appropriate amount was immersed in methyl ethyl ketone, and the time until beautiful peeling was measured. The results of the foregoing tests are shown in Tables 1 to 3, respectively. As clarified by the results shown in Tables 1 and 2, if a monofunctional acrylate having a hydroxyl group and an aromatic ring is used in the resin composition due to photo radical polymerization according to the present invention, the fine tooth pitch The silver electrode also exhibits sufficient electrode protection effects, and can achieve adhesion to glass, film substrates, and the like, and reduce bending of the substrate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and learned that ① higher migration prevention effects can be achieved by adding epoxy resin, ② more effective by adding epoxy resin, saturated polyester resin, and silane coupling agent Adhesion of the adherend, ③ By adding epoxy resin and saturated polyester resin, bending can be further reduced, and ④ By adding saturated polyester resin, recovery can be improved. Example 1 8 to 2 4. Comparative Examples 7 and 8 Each component shown in Table 4 was mixed with a stirring device at a specified ratio, and the activation energy ray-curable resin composition of each component composition was adjusted. For each resin composition processed and prepared in this way, the aforementioned evaluation method is adopted —---- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public 530079 A7 ___B7) V. Description of the invention (23) Evaluation by the same method Water absorption, migration resistance, and adhesion (to a glass substrate). Alas, each resin composition is an ultraviolet irradiation device (Oak Manufacturing Co., Ltd. metal halide lamp), and the irradiation amount is 20000 m J / cm 2 Hardening. The combined test results are shown in Table 4. ---------: II _ -install i — (Please read the precautions on the back before filling this page) · Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The printed paper is also applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 530079 A7 _____B7 V. Description of the invention (25) As explained in the results shown in Table 4, if according to the present invention, in the light Adding an epoxy resin to the radically polymerizable resin composition as a water-repellent adhesive can also achieve sufficient electrode protection effects for silver electrodes with fine pitches. It is also known that ① it can also be used in epoxy resins. Structure with less ionic residue To achieve a higher migration prevention effect, ② use the cross-linking component as a radical polymerization component with a base group of 1 to prevent a decrease in adhesion, and ③ by adding a saturated polyester resin, it can further improve the resistance to adhesion. The effect of the invention is as described above. According to the present invention, the advantages of the UV-curable resin composition can be maintained and its disadvantages can be solved, and water repellency and adhesion to the substrate can be provided. 2. Active energy ray-curable resin composition that is also excellent in migration resistance. Therefore, the active energy ray-curable resin composition of the present invention has better workability than the conventional heat-curable and room-temperature-curable resin compositions. It is used as an active energy hardening type adhesive and coating agent with excellent adhesion to various adherends and various electrodes to prevent migration. (Please read the precautions on the back before filling this page) · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇〇Tv This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Patent No. 89127271 Case-Application date is only Q year 1Q R Case No. «Q197971 Category C〇 ^ L ^ 3 / d〇; ^ Ί / 〇 ^ The above columns are filled by this Office) The Chinese manual amendment page for the people _ 私 every 1 month : ¾ As a supplement, A4 C4 530079 Patent Specification Chinese Invention Name English Name Nationality Activation Energy Ray Hardening Resin Composition

RESIN COMPOSITION CURABLE WITH ACTINIC ENERGY RAY (1) Keinuma Keiko 0 Arima Seifu (1) Shinjo, Kumagaya City, Saitama Prefecture, Japan 1152 2149, 1 Invention 1 ^ People's Residence, Residence (2) Saitama Prefecture, Japan Kawagoe City, 2521, Wakada Honmachi (: 1240 Name (Name) Nationality (1) Taiyo Ink Manufacturing Co., Ltd. Taiyoo Cow Manufacturing Co., Ltd. Line Applicant Residence, Residence (Office) Name of Representative (1) Japan (1) No. 7-chome, Hajimeji-chome, Nerima-ku, Tokyo, Japan (1) Mitsuo Kawahara This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) 530079

A7 Q \ \ l S __B7 1. V. Description of the invention (3) Means to solve the problem (please read the notes on the back before filling this page) In order to achieve the aforementioned purpose, according to the present invention, it is provided to contain (A ) The activation energy ray-curable resin composition of the activation energy ray-curable resin and (B) the photoradical polymerization initiator, in a first aspect, 50% by weight or more of the (A) component is (A > It is characterized by having a radically polymerizable ethylenically unsaturated double bond, one or more hydroxyl groups and an activation energy ray-curable resin composition of an aromatic ring. In the second aspect, the (A) component It is (A 〃) an activation energy ray hardening resin having an ethylenically unsaturated double bond in the molecule, and it is characterized by containing (C) epoxy resin. In the aforementioned second aspect, epoxy resin (C) must be contained, but it is preferable that the first aspect also contains epoxy resin (C). The epoxy resin (C) preferably has a softening point of 40 ° C or higher and is semi-solid or solid at room temperature. In a more preferred aspect, the active energy ray-curable resin composition of the present invention is selected from the group consisting of (D) saturated polyester resin, (E) vinyl tri-cultivated derivative, and (F) silane coupling agent. One. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the active energy ray-curable resin composition of the present invention containing the aforementioned ingredients. For this reason, the previous heat-curable and room-temperature-curable resin compositions have good workability and water repellency. Good adhesion to various adherends and excellent migration prevention effect for various electrodes. Implementation of the invention Plastic bear The active energy ray-curable resin composition of the present invention is in the first aspect. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -6-530079 A7 B7 V. Description of the invention (4) (Please read the precautions on the back before filling in this page) The activation energy ray hardening resin (A) is an ethylenically unsaturated double bond with a free radical polymerizability in the molecule, and more than one hydroxyl group and aromatic The activation energy ray-curable resin (A /) of the ring is an essential constituent, and it is characteristic that the component (A) contains 50% by weight or more. The activation energy ray hardening resin (A >) is to limit the number of functional groups (ethylenically unsaturated double bonds) participating in the photohardening reaction to one in one molecule, so that the effect of hardening shrinkage during photoradical polymerization is reduced. To a minimum, it helps prevent a decrease in adhesion. In addition, the presence of a hydroxyl group greatly contributes to adhesion to a substrate, and the presence of an aromatic ring contributes to water resistance. The above-mentioned activation energy ray-curable resin (A /) may be a monofunctional epoxy (meth) acrylate which is easily available in industry, and the glycidyl group of the monofunctional epoxy resin may be given according to a general manufacturing method ( (Meth) acrylated. Specific examples include (meth) acrylates such as phenyl glycidyl ether, o-biphenyl glycidyl ether, and naphthyl glycidyl ether. Particularly, the (meth) acrylate compound represented by the following general formula (1) or (2) of the novel activation energy ray-curable resin, specifically, o-biphenyl glycidyl ether, naphthyl glycidyl ether The (meth) acrylate is excellent in water repellency. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 (210X297 mm) 530079 A7 to B7 i ^ V. Description of the invention (7) Water glyceryl ether, naphthyl glycidyl ether, phenyl glycidyl ether (methyl) ) Acrylate. (Please read the precautions on the back before filling in this page) 尙 As long as it does not adversely affect the hardening and shrinkage of the composition, that is, within the range of less than 20% by weight of the entire (A) component, it may be Active energy ray hardening resin with two or more ethylenically unsaturated double bonds in the molecule. The photoradical polymerization initiator (B) is not particularly limited as long as it is a compound capable of radically polymerizing the aforementioned activation energy ray-curable resin (A) via an activation energy ray. Specific examples of the photo-radical polymerization initiator (B) include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro group printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Thioxanthones such as thioxanthone, 2,4-diisopropylthioxanthone, etc .; 2-methylanthracene Squin, 2-ethylanthraquinone, 2-second butyl onionquinone, 1-chloro group Anthraquinones such as anthraquinones; 4,4 / benzophenones such as bisdiethylaminobenzophenone; 1 trimethyl-cyclohexyl-phenyl ketone, 2-trimethyl-1, 2-methyl-1 Α-Hydroxyketones such as phenylpropane-l-one; (Bis) phosphoranyl oxides such as 2,4,6-trimethylbenzidine diphenylphosphine oxide; bis (2,4 —Cyclopentadiene-1, 1-yl) bis (2,6—difluoro-3— (1 吡 -pyrrole-1—yl) phenyl) titanium, etc .; 2—Benzyl—2—dimethyl Amino-1— (4-morpholinylphenyl) butanone-1, 2-methyl-1— [4- (methylthio) phenyl] -2—morpholinpropane-1 monoketone and other aminoethyl groups Benzenes; benzyl, 4'4 > α-diketones such as dimethoxybenzyl, catalin-quinone and the like. In addition, the aforementioned photo-radical polymerization initiator (B) may be used in several types depending on the light source used, for example, 2-methyl-1-[4 This paper size is applicable to Chinese National Standards (CNS) Α4 specification (210X297 mm) -10- 530079 A7 B7

V. Description of the invention (8- (methylthio) phenyl]-2 -morpholine-propanone- 1 Acetones such as ketones and thioxanthone or aminoacetophenone; 1- Hydroxy-cyclohexyl-phenyl ketone, etc., a combination of ^ one hydroxy ketones and 2,4,6 trimethyl benzoate, etc. In addition, triethyl methacrylic acid, fluorene diphenyl phosphine oxide, etc. ( Di) fluorenylphosphine oxides and photoinitiation of tertiary amines such as alcohol amines, dimethylaminoisobenzoate, dimethylaminoethyl etc., which are known and commonly used photoradical polymerization initiators In the photoradical polymerization initiator (B) as mentioned above, 2-hydroxy-1, 2-methyl-1, 1-phenylpropane, 1-one, 1-hydroxy-cyclohexylphenyl ketone, 1 Mono (4-isopropylphenyl) -2-hydroxy-2—methylpropane-1-one, 2-methyl-1- [4-mono (methylthio) phenyl] -2-morpholinyl —1-ketone, 2-benzyl-2-dimethylamino—1- (4-morpholinophenyl) butanone—1- and other phenyl ketone compounds, bis (2,4,6-trimethyl) Benzyl amidino) phenylphosphine oxide, etc. (Please read the precautions on the back before filling out this page) • Binding and printing of double-printed fluorenyl phosphine oxides and titanium compounds by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. These photo-radical polymerization initiation The blending of the agent (B) is preferably 100 parts by weight or more and 20 parts by weight or less of the active energy ray-curable resin (A), and preferably 0 parts. The compounding amount of the photoradical polymerization initiator (B) If it is not in the amount, the light hardening cannot be sufficiently performed with the activation energy line, and if it is compounded in a large amount exceeding 20 parts by weight, it is uneconomical because it is hardened, and on the contrary, the properties of the composition after light hardening may be reduced. The amount of the active energy ray hardening resin composition of the invention is 0.5 weight • 5 to 5 weight and 0 5 weight relative to the former. On the one hand, even in the saturated state, it remains and hardens in the second aspect of the paper. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) -11-530079 A7 B7 V. Description of invention (11)

〇 一 (a) CH—CH2 \ / 〇

0— (b) CH-CH; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. Examples of such epoxy resins include Ceroxide 3150 and Ceroxide 2085 manufactured by Diacel Chemical Industry Co., Ltd. The polyether type epoxy resin having the functional group represented by the above general formula (3) can make a compound having active hydrogen and 4-vinylcyclohexene 1-oxide, or a compound having one other epoxy group as necessary 'The vinyl group of the polyether compound obtained by the reaction in the presence of a catalyst can be obtained by partial or complete epoxidation with peracids such as peracetic acid and hydrogen peroxide. In this case, a small amount of ethenyl or the like may be introduced. The compounds having active hydrogen are alcohols, and examples thereof include linear or branched aliphatic alcohols, preferably polyhydric alcohols such as trihydroxymethylpropane, and phenols, carboxylic acids, amines, and thiols. . Among these compounds having active hydrogen, it is not limited to the introduction of only one functional group represented by the aforementioned general formula (3), and several may be introduced. However, in the case where several are introduced, if the number of the overlapping portions of the aforementioned functional group is too large, it will become a compound with a high melting point, so the total count is preferably 100 or less. In addition, other polyether-type epoxy resins described in Japanese Patent No. 7-2 5 8 6 4 may be used. Since such a polyether-type epoxy resin has been described in detail in the aforementioned bulletin, it is referred to the aforementioned bulletin in detail. The compounding amount of these epoxy resins (C) is preferably 5 parts by weight or more and 60 parts by weight or less with respect to 1,000 parts by weight of the activation energy ray-curable resin (A), and preferably 5 to 4 parts. 0 parts by weight. Epoxy resin ((Please read the precautions on the back before filling in this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 530079 A7 1¾ iL 2T _ B7 _: _- V. Invention Note (12) C) If the blending amount is less than 5 parts by weight, it is difficult to achieve the aforementioned effect. On the other hand, a large amount of more than 60 parts by weight is also saturated due to the expected effect (please read the precautions on the back before filling in This page) state is not economical, and it may interfere with the photo-curability of the composition. The activation energy ray-curable resin composition of the present invention is added to the above components, and a saturated polyester resin ( D) is better. The purpose of this saturated polyester tree (D) is not particularly limited as long as it has an effect of improving the adhesion with the adherend. Specific examples of the saturated polyester resin (D) include Viron 2 0 0, 220, 240, 245, 270, 280, 290, 296, 300, 500, 530, and 550 of the Toyobo Viron series (manufactured by Toyobo Co., Ltd.). , 560, 600, 630, 650, BX1001, GK110, 130, 140, 150, 180, 190, 250, 330, 590, 640, 680, 780, 810, 8 8 0, 8 9 0, etc. Furthermore, in addition to the effect of improving the adhesiveness of such saturated polyester films, they also have excellent recovery properties that allow the cured product to be easily peeled from the substrate. The blending amount of the saturated polyester resin (D) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is more than 5 parts by weight and less than 50 parts by weight relative to the aforementioned active energy ray-curable resin (A) 100 parts by weight As appropriate, it is preferably 5 to 30 parts by weight. It is difficult to achieve the aforementioned effect if the blending amount of saturated polyester tree (D) is less than 5 parts by weight. On the other hand, even if it is blended in a large amount exceeding 50 parts by weight, it is saturated because of the expected effect, so it is not necessary. It is economical, and it may prevent the composition of the paper from being applied to the Chinese National Standard (CMS) A4 specification (2 丨 〇X 297mm) -15- 530079 A7 _ B7 points 丨 Fifth, the light hardening of the invention (13) Properties, reducing the properties of the hardened material. (Please read the precautions on the back before filling out this page) The active energy ray-curable resin composition of the present invention is in the above-mentioned components, and it is better to add a vinyl Sanka derivative (E). The purpose of using this vinyl trioxane derivative (E) is to effectively prevent migration of metal electrodes. Specific examples of the vinyltriphine derivative (E) include 2,4-diamino-6-vinyl-S-triphine, 2,4-diamino-6-methacryloxy-S -Trimorph and its isocyanurate adduct. These vinyl-based three-farming compounds or their derivatives (E) are provided for use alone or in a mixture of two or more kinds. The blending amount of these vinyl three-cultivated derivatives (E) is preferably 0.5 to 20 parts by weight, and more preferably 0.5 to 50 parts by weight of the activation energy ray-curable resin (A). ~ 5 parts by weight. It is difficult to sufficiently improve the migration resistance effect when the compounding amount of the vinyl trident derivative (E) is less than 0.5 parts by weight. On the other hand, even if the compounding amount exceeds 20 parts by weight, the expected effect is saturated. Therefore, it is not economical, and, on the contrary, it is feared that the composition will remain after light hardening, which will reduce the characteristics of the hardened material. Printed by the Intellectual Property of the Ministry of Economic Affairs and the Consumers' Cooperative, the activated energy ray-curable resin composition of the present invention may contain a silane coupling agent (F) as required. The purpose of adding the silane coupling agent (F) is to improve the adhesion with the substrate, especially with glass. The silane coupling agent (F) is not particularly limited as long as it can improve the adhesion to the substrate. Specific examples of the silane coupling agent (F) include A-143, A-150, A-151, A-171, A-172, A-174, A-186, A-187, manufactured by Unica Co., Ltd., Japan. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297mm) -16- 530079 A7 B7 V. Description of invention (17)

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7 B ^ 1¾ 修 a 0 V. Description of the invention (18) Table 2 Composition (parts by weight) and characteristics Example 10 11 12 13 14 15 16 17 A Al 100 100 100 100 100 100 100 100 A-2 — A-3 — K " ΡΕΑ * υ — L-4 * 2) — — — — — — One — A " TMPTA * 3) One — — — — One — — B IRUGACURE 184 * 4) 3 3 3 3 3 3 3 3 C YX-4000 * 5) EOCN 1020 * 6) — — 15 — — 15 70 — Ceroxide 3150 * 7) — — — 15 — — — — D Viron 200 * 8) 10 — — — 10 10 — 65 F A-174 * 9) — 1 — 1 1 1 — — Water absorption (%) 0.30 0.32 0.28 0.26 0.30 0.2 0.36 0.38 Migration resistance (hr) 1000 1000 1200 1500 1000 1200 800 800 Adhesive glass 〇 ◎ ○ ◎ ◎ Δ Δ Δ PET ◎ ○ ◎ ◎ ◎ Δ Δ Bend ◎ ○ ◎ ◎ ◎ ◎ 〇 Recoverability (minutes) 5 15 5 10 5 5 10 5 Note * 1) Phenoxyethyl acrylate (please read the precautions on the back first) Fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * 2) 2-Phenylphenoloxysilane Adduct Monopropene Acid ester (manufactured by Shin Nakamura Chemical Co., Ltd.) * 3) trimethylolpropane triacrylate * 4) photoradical polymerization bow manufactured by Coba Specialty Chemicals Co., Ltd. hair extension agent: 1-yl-cyclohexyl-benzene Ketone * 5) Bisphenol-type solid epoxy resin made by Oleochemical Shell Epoxy Co., Ltd. * 6) Nippon Kayaku ㈱) Polyglycidyl ether of o-cresol novolak lacquer * 7) Diacd Chemical Industry Saturated polyester shed made from 2,2- (hydroxymethyl) -butanol-1,2-epoxy-4 (2′f-based) cyclohexanone adduct * 8 frozen ocean textile company) Purpose * 9) Silane coupling agent made by Umca Co., Ltd. of Japan: r-methacryloxypropyltrimethoxysilane __ This paper size applies to China National Standard (CNS) A4 specification (2) 0X297 mm -21- 530079 A7 B7 丨 f. 5. Description of the invention (I9) Table 3 Composition (parts by weight) and characteristics Comparative Example 1 2 3 4 5 6 A Al — — — 40 — A-2 — — — 40 — — A-3 — — — — — 40 Ar / PEA * 1) — 10 — 60 — — L-4 * 2) — — 100 — — 60 A7 / tmpta * 3) 100 — — — 60 — B IRUGACURE 184 * 4) 3 3 3 3 3 3 C YX-4000 * 5) — — — — — — EOCN 1020 * 6) — — — — — Ceroxide 3150 + 7) — — — — — — D Viron 200 * 8) — — — — — — F A-174 * 9) — — — — — — Water absorption (%) 0.21 0.32 0.26 0.27 0.26 0.28 Resistance Mobility (hr) — 800 500 800 — 600 Adhesive glass X Δ Δ Δ X Δ PET XXXXXX Bend X 〇X 〇XX Recovery (minutes) — 15 15 15 — 15 Preparation * 1) Phenoxyethyl acrylate (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * 2) 2-Phenylphenoloxysilane-based monoacrylate (made by Shin Nakamura Chemical Co., Ltd.) * 3) Trishydroxypropylpropane triacrylate * 4) Photo radical polymerization initiator manufactured by Coba Specialty Chemicals Co., Ltd .: 1-hydroxy-cyclohexyl-phenyl ketone * 5) Oily Shell Epoxy Co., Ltd. Phenol-type solid epoxy resin * 6) Polyglycidyl ether of o-cresol novolak lacquer manufactured by Nippon Kayaku Co., Ltd. * 7) 2,2- (hydroxymethyl) butyl diamine manufactured by Diacel Chemical Industry Co., Ltd. Alcohol 1,2-epoxy-4 (2 Feng Yuanji) cyclohexanone adducts * 8 Saturated polyester tree made by Hanyobo Co., Ltd. * 9) Silane coupling agent made by Ubenca Umca: r -A Acryloxypropyltrimethoxysilane_ This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -22- 530079 A7 Tenon B7 5. Description of the invention (2〇) (Please read the note on the back first Please fill in this page again for each item) For each resin composition prepared in this way, the water absorption, migration resistance, adhesion, bending, and repairability were evaluated. The evaluation method is as follows. In other words, each resin composition was cured using an ultraviolet irradiation device (Oak Manufacturing Co., Ltd. metal halide lamp) at an irradiation amount of 2000 m J / cm 2. (1) Water absorption:

Each resin composition sample was poured into a circular Teflon container having a diameter of 150 mm and a depth of 2 mm, and was then hardened to prepare a nine-piece for measurement. After measuring the weight (a) of the nine materials for measurement, it was immersed in ion-exchanged water at 20 t for 24 hours, and the weight (b) after immersion was measured. The water absorption rate at this time is the 値 (%) obtained from ((b)-(a)) / (a) X 1 0 0. (2) Migration resistance test: On a Corming 1737 glass plate (thickness 0_7 mm) as a test substrate, a comb-type electrode was prepared from a commercially available calcined silver paste (L / S = 100 / 100 // m) for use. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the comb-shaped electrode of the test substrate, coated each resin composition with a thickness of 2 mm, and a constant temperature and humidity bath at a temperature of 85 ° C and a relative humidity of 85%. Leave for 15 hours. At this time, the applied voltage of the comb-shaped electrode was DC 100 V, and the insulation resistance in the constant temperature and humidity tank was measured at any time. The evaluation of the migration resistance was shown as the insulation resistance in the foregoing measurement. 1 · 0 X 1 0 A moment below 5 Ω is considered a short circuit, and the evaluation test is based on the Chinese national standard (CNS) A4 specification (210X297 mm) -23- 530079 A7% B7 V. Description of the invention (24) Intellectual property of the Ministry of Economic Affairs ^ 7 Comparative example printed by employee consumer cooperatives 〇〇〇1 T- < I 1 0 * 3 1 1 1 1 I 0.27 〇1 1 CO 1 1 1 1 1 1 0.29 B f =: X Example 〇1 1 CO 1 1 1 1 1 " H CM 0.29 1500 or more ◎ CO 05 § 1 1 1 1 1 VO fH 1 0.29 | 1500 or more 1 ◎ CN 03 § 1 CO 1 1 1 I r- < 1 0.27 1500 or more. 1 8 1 cn 1 1 1 1 1-H 1 0.30 1200 〇〇1 1 cn 1 1 1 1 1 1 0.28 1200 〇ON § '1 cn 1 1 1 1 1 1 0.27 1000 〇〇〇§ | 1 cn 1 I 1 I 1 1 0.30 1000 〇I Composition (parts by weight) and characteristics PEA * 0 eoa * 2) TMPTA · 3) IRUGACURE 184 * 4) | SP150,5) YX-4000 · 6) | EOCN 1020 ^ | Ceroxide 315 ( Γ Viron 200,9) a > A-174 · 1〗) Water absorption (%) Migration resistance (hr) Adhesiveness (glass) < u Q PQ Pin iwsissr 篛 sin ^ 籴 account w 燧 side feed® 菡 枨fr- »a! (#) booth ^ 柃 [11 (卜 * ¾¾ 秘 酹 到 画 副 s 擀 ®fi) ispqipqsrvlse * ISAlM» -srIJ®-wli-I " g 鹬 一 & < 0 account ««来 来 if («) sl ^ io ☆ so ^ s ^ oofI— ow 舻 _gsMg Alkaline roll 氍 发 1E (U1 0 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) (please read the back first) (Please fill out this page again) — »Install ·

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530079-- A8 B8 C8 D8 Patent Application No. 89 127271 Patent Application Chinese Patent Application Amendment of the Republic of China 9 丨 莘 P 葡 多 正 1. An active energy ray hardening resin group -L ± ^ dl which contains (A) active energy ray hardening The resin and the activation energy ray-curable resin composition of the (B) photoradical polymerization initiator are characterized in that 50% by mass or more of the (A) component is (A /) having one radical polymerizability in the molecule The activation energy ray-curable resin composition of an ethylenically unsaturated double bond, one or more hydroxyl groups and an aromatic ring, the activation energy ray-curable resin (A /) is represented by the following general formula (1) or (2) Shown (meth) acrylate compounds: (R1). (1) (R2), printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (R2) (R1) (wherein X is a hydrogen atom or a methyl group, Y is C (CΗ3), -SOCΗ2 — or (2) R1 and R2 are carbon numbers 1 to 1 2 For each linear, cyclic or branched courtyard, m is an integer from 0 to 4, and η is an integer from 0 to 5) 'and 100 parts by weight of the (A) activation energy ray-curable resin' ( (Please read the notes on the back before filling out this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 530079 A8 B8 C8 D8 6. Scope of patent application The blending amount of the (B) photo-radical polymerization initiator is 0.5 parts by weight or more and 20 weight The following. (Please read the notes on the back before filling out this page) 2 · If the composition in the scope of patent application No. 1 contains (C) epoxy resin. 3. An activation energy ray-curable resin composition comprising an activation energy ray-curable resin composition containing (A) an activation energy ray-curable resin and (B) a photoradical polymerization initiator, characterized in that The component (A) is an activation energy ray-curable resin (A 〃) having an ethylenically unsaturated double bond in the molecule, and further contains (C) epoxy resin. The activation energy ray-curable resin (A 〃) is Monofunctional (meth) acrylic esters, the blending amount of the (B) photoradical polymerization initiator is 0.5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the (A) activating energy ray-curable resin. 'The blending amount of the epoxy resin (C) is 5 parts by weight or more and 60 parts by weight or less, the softening point of the epoxy resin (C) is 40 ° C or more, and the resin is semi-solid at room temperature. Or solid state. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 · If the composition of any one of the items 1 to 3 of the patent application scope, it further contains three wells selected from (D) saturated polyester resin and (E) vinyl At least one of a group of a derivative and (F) a silane coupling agent. 5. The composition according to item 3 of the scope of patent application, wherein the aforementioned epoxy resin (C) is an epoxy compound having a partial structure represented by the following general formula (3) in one molecule, or having the following formula ( 4) or (5) alicyclic epoxy compounds of any of the structures shown: This paper size applies to Chinese national standard (CNS> A4 specification (210X297 mm) _ 2-530079 A8 B8 C8 D8 scope of patent application (3) 〇Cr (4) 〇⑸ (where χ is an epoxy group and / or a vinyl group, and P is an integer of 1 to 100, but the molecule contains at least one epoxy group.) 6 The composition of the scope of application for patent No. 4, wherein the aforementioned vinyltriphine derivative (E) is composed of 2,4-diamino-6-vinyl-S-three, and 2,4-diamine-6 -Methacryloxy-S-Three Cultivation and at least one selected from the group consisting of isocyanuric acid adducts. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 3-