Anti-static adhesive cured material

Abstract

The invention relates to an anti-static adhesion cured product, which comprises a (methyl) acrylate polymer with carboxylic acid and organic nitrogen base with a plurality of reactive nitrogen. The (meth) acrylate polymer is formed by reaction of reaction components including the composition, a cross-linking agent having a plurality of (meth) acrylate functional groups, and a photoinitiator. The composition comprises 54 to 90 wt% of alkyl (meth) acrylate, 10 to 45 wt% of a non-acidic hydrophilic ethylene compound and an acidic (meth) acryloyloxy compound. Based on the total amount of 100 parts by weight of the composition, the amount of the crosslinking agent having a plurality of (meth) acrylate functional groups is 0.05-2 parts by weight, the amount of the photoinitiator is less than 1 part by weight, and the total amount of the organic nitrogen base having a plurality of reactive nitrogen and the acidic (meth) acryloyloxy compound is 0.4-4 parts by weight. The reactive nitrogen of the organic nitrogen base having a plurality of reactive nitrogen atoms is bonded by an ionic bond to the carboxylic acid of the (meth) acrylate polymer having the carboxylic acid.

Description

TECHNICAL FIELD

[0001] The present application relates to a cured product, and in particular to an antistatic adhesive cured product. BACKGROUND

[0002] Taiwanese Patent Publication No. 202311476 discloses an adhesive composition, and the adhesive composition includes a (meth)acrylic polymer, an antistatic agent, a crosslinking agent having an acrylate functional group, a silane coupling agent, and a solvent. The (meth)acrylic polymer is formed by a polymerization reaction of a monomer mixture, and the monomer mixture includes an alkyl (meth)acrylate and a copolymerizable monomer. The copolymerizable monomer is, for example, a monomer having a hydroxyl group or a monomer having a nitrogen atom, but substantially does not include a monomer having a carboxyl group. The antistatic agent is an ionic compound, and has a functional group capable of forming a covalent bond with the (meth)acrylic polymer, such as a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, an allyl group, a styryl group, a hydroxyl group, an amino group, a mercapto group, or an epoxy group.

[0003] Although the adhesive composition of the patent publication can form an antistatic adhesive sheet having a low surface resistance, when the antistatic adhesive sheet is used for a product formed by attaching an adherend, the antistatic adhesive sheet is easily separated from the adherend at the attachment portion of the antistatic adhesive sheet and the adherend under high-temperature (for example, 80°C) environmental conditions, so that the antistatic adhesive sheet is difficult to be stably attached to the adherend. Therefore, the antistatic adhesive sheet has a problem of poor heat resistance. SUMMARY

[0004] The present application relates to a cured product, and in particular to an antistatic adhesive cured product.

[0005] The antistatic adhesive cured product of the present invention includes a (meth)acrylate polymer having a carboxylic acid (A) and an organic nitrogen base having two or more reactive nitrogens (B). The (meth)acrylate polymer having a carboxylic acid (A) is formed by polymerization of reaction components including a composition, a crosslinking agent having two or more (meth)acrylate functional groups (a-4), and a photoinitiator (a-5). The composition includes 54 to 90 wt% of an alkyl (meth)acrylate (a-1), 10 to 45 wt% of a non-acidic hydrophilic vinylic compound (a-2), and an acidic (meth)acryloyloxy compound (a-3). The amount of the crosslinking agent having two or more (meth)acrylate functional groups (a-4) is 0.05 to 2 parts by weight, and the amount of the photoinitiator (a-5) is 1 part by weight or less, based on 100 parts by weight of the total amount of the composition. The reactive nitrogens of the organic nitrogen base having two or more reactive nitrogens (B) are ionically bonded to the carboxylic acid of the (meth)acrylate polymer having a carboxylic acid (A), and the total amount of the organic nitrogen base having two or more reactive nitrogens (B) and the acidic (meth)acryloyloxy compound (a-3) is 0.4 to 4 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0006] The antistatic adhesive cured product of the present invention has a molar ratio of the organic nitrogen base having two or more reactive nitrogens (B) to the acidic (meth)acryloyloxy compound (a-3) of 1:3 to 3:1.

[0007] The antistatic adhesive cured product of the present invention has the organic nitrogen base having two or more reactive nitrogens (B) selected from the group consisting of 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane, 1-(2-aminoethyl)piperazine, (2,2'-diaminodiethyl)amine, and combinations thereof.

[0008] The antistatic adhesive cured product of the present invention has the acidic (meth)acryloyloxy compound (a-3) selected from the group consisting of (meth)acrylic acid, (meth)acrylate having a carboxylic acid, and combinations thereof.

[0009] The antistatic adhesive cured product of the present invention has the non-acidic hydrophilic vinylic compound (a-2) selected from the group consisting of (meth)acrylate having a hydroxyl group, acrylamide-based compound, N-vinylamide-based compound, (meth)acrylate having an ether group, and combinations thereof.

[0010] The antistatic adhesive cured product of the present invention has the reaction components further including a silane coupling agent (a-7).

[0011] The antistatic adhesive cured product of the present invention has the silane coupling agent (a-7) in an amount of 0.1 to 1 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0012] The antistatic adhesive cured product of the present application, the reaction component further comprises a chain transfer agent (a-6).

[0013] The antistatic adhesive cured product of the present application, the content of the (meth) acrylate alkyl ester (a-1) is 54 wt% to 85 wt% based on the total amount of the composition being 100 wt%.

[0014] The antistatic adhesive cured product of the present application, the content of the non-acidic hydrophilic ethylene compound (a-2) is 15 wt% to 45 wt% based on the total amount of the composition being 100 wt%.

[0015] The antistatic adhesive cured product of the present application, the content of the non-acidic hydrophilic ethylene compound (a-2) is 15 wt% to 45 wt% based on the total amount of the composition being 100 wt%. 13 Ω / □below), and the antistatic adhesive cured product used in the product formed after being attached to the adherend (such as a polycarbonate sheet) is not easily separated from the adherend at high temperature (such as 80℃ or higher) environment conditions, and the antistatic adhesive cured product is firmly attached to the adherend, thus the antistatic adhesive cured product has good heat resistance. DETAILED DESCRIPTION

[0016] The present application is described in detail below.

[0017] The present application relates to an antistatic adhesive cured product. The antistatic adhesive cured product comprises a (meth)acrylate polymer having a carboxylic acid (A) and an organic nitrogen base having two or more reactive nitrogens (B). The (meth)acrylate polymer having a carboxylic acid (A) is formed by a polymerization reaction of reaction components including a composition, a crosslinking agent having two or more (meth)acrylate functional groups (a-4), and a photoinitiator (a-5). The composition includes 54 to 90 wt% of a (meth)acrylic alkyl ester (a-1), 10 to 45 wt% of a non-acidic hydrophilic vinylic compound (a-2), and an acidic (meth)acryloyloxy compound (a-3), based on 100 wt% of the total amount of the composition. The crosslinking agent having two or more (meth)acrylate functional groups (a-4) is 0.05 to 2 parts by weight, and the photoinitiator (a-5) is 1 part by weight or less, based on 100 parts by weight of the total amount of the composition. The reactive nitrogen of the organic nitrogen base having two or more reactive nitrogens (B) is ionically bonded to the carboxylic acid of the (meth)acrylate polymer having a carboxylic acid (A), and the total amount of the organic nitrogen base having two or more reactive nitrogens (B) and the acidic (meth)acryloyloxy compound (a-3) is 0.4 to 4 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0018] <The (meth)acrylate polymer having a carboxylic acid (A)>

[0019] The carboxylic acid in the (meth)acrylate polymer having a carboxylic acid (A) is from the acidic (meth)acryloyloxy compound (a-3).

[0020] <The (meth)acrylic alkyl ester (a-1)>

[0021] In some embodiments of the present application, the content of the (meth)acrylic alkyl ester (a-1) is 54 to 85 wt%, based on 100 wt% of the total amount of the composition. The (meth)acrylic alkyl ester (a-1) can be used alone or in a mixture, and the (meth)acrylic alkyl ester (a-1) is, for example, but not limited to, ethyl propylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, (2-ethyl)hexyl acrylate, or (2-ethyl)hexyl methacrylate, etc.

[0022] <The non-acidic hydrophilic vinylic compound (a-2)>

[0023] In some embodiments of the present application, the content of the non-acidic hydrophilic vinylic compound (a-2) is 15 to 45 wt% based on the total amount of the composition. The non-acidic hydrophilic vinylic compound (a-2) can be used alone or in a mixture of two or more, and the non-acidic hydrophilic vinylic compound (a-2) is, for example, but not limited to, a (meth)acrylate having a hydroxyl group, an acrylamide-based compound, an N-vinylamide-based compound, or a (meth)acrylate having an ether group, etc. The (meth)acrylate having a hydroxyl group is, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, or hydroxybutyl methacrylate, etc. The acrylamide-based compound is, for example, acrylamide. The N-vinylamide-based compound is, for example, N-vinyl-2-pyrrolidone. The (meth)acrylate having an ether group is, for example, tetrahydrofurfuryl acrylate, etc.

[0024] <acidic (meth)acryloyloxy compound (a-3)>

[0025] The acidic (meth)acryloyloxy compound (a-3) can be used alone or in a mixture of two or more, and the acidic (meth)acryloyloxy compound (a-3) is, for example, but not limited to, (meth)acrylic acid or a (meth)acrylate having a carboxylic acid, etc. In some embodiments of the present application, the acidic (meth)acryloyloxy compound (a-3) is selected from (meth)acrylic acid, a (meth)acrylate having a carboxylic acid, or a combination thereof. The (meth)acrylate having a carboxylic acid is, for example, but not limited to, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-methacryloyloxyethyl phthalate, etc. In some embodiments of the present application, the content of the acidic (meth)acryloyloxy compound (a-3) is 0.1 to 2 wt% based on the total amount of the composition. In some embodiments of the present application, the content of the acidic (meth)acryloyloxy compound (a-3) is 0.15 to 1.3 wt% based on the total amount of the composition.

[0026] <crosslinking agent having two or more (meth)acrylate functional groups (a-4)>

[0027] The crosslinking agent having two or more (meth)acrylate functional groups (a-4) can be used alone or in a mixture of a plurality of kinds, and the crosslinking agent having two or more (meth)acrylate functional groups (a-4) is, for example, but not limited to, 1,6-hexanediol diacrylate or ethoxylated (20) trimethylolpropane triacrylate, and the like. In some embodiments of the present application, the content of the crosslinking agent having two or more (meth)acrylate functional groups is 0.05 parts by weight to 0.2 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0028] <Photoinitiator (a-5)>

[0029] The photoinitiator (a-5) can be used alone or in a mixture of a plurality of kinds, and the photoinitiator (a-5) is, for example, but not limited to, 1-hydroxycyclohexyl phenyl ketone or 2,2-dimethoxy-2-phenylacetophenone, and the like. The 1-hydroxycyclohexyl phenyl ketone is, for example, a commercially available product of the brand IGM Resins, and the model number is IGM 184 of the Netherlands IGM Resins Co., Ltd. The 2,2-dimethoxy-2-phenylacetophenone is, for example, a commercially available product of the brand IGM Resins, and the model number is IGM 651 of the Netherlands IGM Resins Co., Ltd. 184 of the Netherlands IGM Resins Co., Ltd. The 2,2-dimethoxy-2-phenylacetophenone is, for example, a commercially available product of the brand IGM Resins, and the model number is IGM 651 of the Netherlands IGM Resins Co., Ltd. 651 of the Netherlands IGM Resins Co., Ltd. In some embodiments of the present application, the content of the photoinitiator (a-5) is 0.01 parts by weight to 1 parts by weight, based on 100 parts by weight of the total amount of the composition. In some embodiments of the present application, the content of the photoinitiator (a-5) is 0.05 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0030] <Chain transfer agent (a-6)>

[0031] In some embodiments of the present application, the reaction component further comprises a chain transfer agent (a-6). The chain transfer agent (a-6) can be used alone or in a mixture of a plurality of kinds, and the chain transfer agent (a-6) is, for example, but not limited to, pentaerythritol tetra(3-mercaptopropionate). In some embodiments of the present application, the content of the chain transfer agent (a-6) is greater than 0 parts by weight and 1 parts by weight or less, based on 100 parts by weight of the total amount of the composition. In some embodiments of the present application, the content of the chain transfer agent (a-6) is greater than 0 parts by weight and 0.5 parts by weight or less, based on 100 parts by weight of the total amount of the composition.

[0032] <Silane coupling agent (a-7)>

[0033] In some embodiments of the present application, the reaction component further comprises a silane coupling agent (a-7). The silane coupling agent (a-7) can be used alone or in a mixture of two or more, and the silane coupling agent (a-7) is, for example, but not limited to, (3-glycidoxypropyl)trimethoxysilane. The (3-glycidoxypropyl)trimethoxysilane is, for example, but not limited to, a commercially available product of the brand Shin-Etsu Chemical Co., Ltd. and the type number KBM403. In some embodiments of the present application, the content of the silane coupling agent (a-7) is 0.1 parts by weight to 1 part by weight, based on 100 parts by weight of the total amount of the composition. In some embodiments of the present application, the content of the silane coupling agent (a-7) is 0.05 parts by weight to 0.1 part by weight, based on 100 parts by weight of the total amount of the composition.

[0034] <Organic nitrogen base (B) having two or more reactive nitrogens>

[0035] The organic nitrogen base (B) having two or more reactive nitrogens can be used alone or in a mixture of two or more, and the organic nitrogen base (B) having two or more reactive nitrogens is, for example, but not limited to, 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane, 1-(2-aminoethyl)piperazine, or (2,2'-diaminodiethylamine), etc. In some embodiments of the present application, the total amount of the organic nitrogen base (B) having two or more reactive nitrogens and the acidic (meth)acryloyloxy compound (a-3) is 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the total amount of the composition.

[0036] The antistatic adhesive cured product is prepared, for example, by Method 1 or Method 2.

[0037] In the Method 1, the antistatic adhesive cured product is formed by a curing reaction of an antistatic adhesive composition. The antistatic adhesive composition comprises a first mixture (X), an organic nitrogen base (B) having two or more reactive nitrogens, an acidic (meth)acryloyloxy compound (a-3), a crosslinking agent (a-4) having two or more (meth)acrylate functional groups, and a photoinitiator (a-5). The first mixture (X) comprises an alkyl (meth)acrylate (a-1) and a non-acidic hydrophilic vinylic compound (a-2).

[0038] In the second method, the antistatic adhesive cured product is formed from an antistatic adhesive composition by a curing reaction. The antistatic adhesive composition includes a second mixture (Y), an organic nitrogen base (B) having two or more reactive nitrogens, a crosslinking agent (a-4) having two or more (meth)acrylate functional groups, and a photoinitiator (a-5). The second mixture (Y) includes an alkyl (meth)acrylate (a-1), a non-acidic hydrophilic vinylic compound (a-2), and an acidic (meth)acryloyloxy compound (a-3).

[0039] In some embodiments of the present application, the antistatic adhesive composition further includes a chain transfer agent (a-6). The chain transfer agent (a-6) can be used alone or in a mixture of two or more, and the chain transfer agent (a-6) is, for example, but not limited to, pentaerythritol tetra(3-mercaptopropionate).

[0040] In some embodiments of the present application, the antistatic adhesive composition further includes a silane coupling agent (a-7). The silane coupling agent (a-7) can be used alone or in a mixture of two or more, and the silane coupling agent (a-7) is, for example, but not limited to, (3-glycidoxypropyl)trimethoxysilane. The (3-glycidoxypropyl)trimethoxysilane is, for example, but not limited to, a commercially available product of the brand name of Shin-Etsu Chemical Co., Ltd. and the model number of KBM403.

[0041] In some embodiments of the present application, the curing reaction is performed by irradiating the antistatic adhesive composition with ultraviolet light, and the cumulative irradiation energy of the ultraviolet light is 2000 mJ / cm 2 to 6000 mJ / cm 2 .In some embodiments of the present application, the curing reaction includes a first-stage photocuring reaction and a second-stage photocuring reaction after the first-stage photocuring reaction. The first-stage photocuring reaction is performed under conditions of irradiation with ultraviolet light having an energy of 10 mW to 30 mW for 30 seconds to 90 seconds, and the second-stage photocuring reaction is performed under conditions of irradiation with ultraviolet light having an energy of 35 mW to 65 mW for 30 seconds to 60 seconds.

[0042] In the present application, the antistatic adhesive cured product not only has a low surface resistance and does not have bubbles, but also can be firmly attached to a substrate without peeling. The substrate is, for example, a polycarbonate substrate, a polymethyl methacrylate substrate, a polyvinyl butyral substrate, a cellulose triacetate substrate, or the like.

[0043] The present application will be further illustrated with the following examples, but it should be understood that the examples are only illustrative and should not be interpreted as limiting the implementation of the present application.

[0044] Preparation Example 1 - First Mixture

[0045] Example 1 - First mixture 55 parts by weight of butyl acrylate, 4 parts by weight of N-vinyl-2-pyrrolidone, 22 parts by weight of hydroxybutyl acrylate, 19 parts by weight of hydroxyethyl acrylate, and 0.01 part by weight of 2,2-dimethoxy-2-phenylacetophenone (as a photoinitiator; brand: IGM Resins, Netherlands; type: IGM 1010) were mixed for 30 minutes under a nitrogen atmosphere at 25°C, and then irradiated with ultraviolet light of a wavelength of 365 nm and subjected to viscosity adjustment processing for 70 seconds at 25°C to obtain a product having a viscosity of 1485 cp and containing the first mixture. The first mixture contained 94.86 wt% of a monomer component (containing 55 wt% of butyl acrylate, 4 wt% of N-vinyl-2-pyrrolidone, 22 wt% of hydroxybutyl acrylate, and 19 wt% of hydroxyethyl acrylate) and 5.14 wt% of a prepolymer (as a thickening agent to adjust the overall fluidity). 651) were mixed for 30 minutes under a nitrogen atmosphere at 25°C, and then irradiated with ultraviolet light of a wavelength of 365 nm and subjected to viscosity adjustment processing for 70 seconds at 25°C to obtain a product having a viscosity of 1485 cp and containing the first mixture. The first mixture contained 94.86 wt% of a monomer component (containing 55 wt% of butyl acrylate, 4 wt% of N-vinyl-2-pyrrolidone, 22 wt% of hydroxybutyl acrylate, and 19 wt% of hydroxyethyl acrylate) and 5.14 wt% of a prepolymer (as a thickening agent to adjust the overall fluidity).

[0046] Preparation Examples 2 to 3

[0047] The preparation methods of the Preparation Examples 2 to 3 were substantially similar to those of the Preparation Example 1, except that the types and amounts of the components were changed as shown in Table 1. In the Preparation Example 2, the monomer component contained 81 wt% of butyl acrylate and 19 wt% of hydroxyethyl acrylate. In the Preparation Example 3, the monomer component contained 70 wt% of butyl acrylate, 10 wt% of N-vinyl-2-pyrrolidone, and 20 wt% of hydroxybutyl acrylate.

[0048] Preparation Example 4 - Second mixture

[0049] Example 1 - First mixture 55 parts by weight of butyl acrylate, 4 parts by weight of N-vinyl-2-pyrrolidone, 22 parts by weight of hydroxybutyl acrylate, 19 parts by weight of hydroxyethyl acrylate, and 0.01 part by weight of 2,2-dimethoxy-2-phenylacetophenone (as a photoinitiator; brand: IGM Resins, Netherlands; type: IGM 1010) were mixed for 30 minutes under a nitrogen atmosphere at 25°C, and then irradiated with ultraviolet light of a wavelength of 365 nm and subjected to viscosity adjustment processing for 70 seconds at 25°C to obtain a product having a viscosity of 1485 cp and containing the first mixture. The first mixture contained 94.86 wt% of a monomer component (containing 55 wt% of butyl acrylate, 4 wt% of N-vinyl-2-pyrrolidone, 22 wt% of hydroxybutyl acrylate, and 19 wt% of hydroxyethyl acrylate) and 5.14 wt% of a prepolymer (as a thickening agent to adjust the overall fluidity). 651) were mixed for 30 minutes under a nitrogen atmosphere at 25°C, and then irradiated with ultraviolet light of a wavelength of 365 nm and subjected to viscosity adjustment processing for 70 seconds at 25°C to obtain a product having a viscosity of 1485 cp and containing the first mixture. The first mixture contained 94.86 wt% of a monomer component (containing 55 wt% of butyl acrylate, 4 wt% of N-vinyl-2-pyrrolidone, 22 wt% of hydroxybutyl acrylate, and 19 wt% of hydroxyethyl acrylate) and 5.14 wt% of a prepolymer (as a thickening agent to adjust the overall fluidity).

[0050] Preparation Examples 5 to 6

[0051] The preparation method of Preparation Examples 5 to 6 is substantially similar to that of Preparation Example 4, except that the types and amounts of the ingredients are changed, as shown in Table 1. In Preparation Example 5, the monomer component comprises 40 wt% of butyl acrylate, 20 wt% of ethyl acrylate, 39.5 wt% of hydroxypropyl acrylate, and 0.5 wt% of ethyl succinate acrylate. In Preparation Example 6, the monomer component comprises 40 wt% of butyl acrylate, 20 wt% of ethyl acrylate, 39.5 wt% of hydroxypropyl acrylate, and 0.5 wt% of ethyl phthalate acrylate.

[0052] Table 1

[0053]

[0054]

[0055] Example 1

[0056] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 0.186 parts by weight of acrylic acid, 0.314 parts by weight of 4-(dimethylamino)pyridine, 0.103 parts by weight of ethoxylated (20) trimethylolpropane triacrylate, 0.08 parts by weight of 1-hydroxycyclohexyl phenyl ketone (brand: IGM Resins, Netherlands; model number: Irgacure® 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model number: Irgacure® 651), and 0.1 parts by weight of (3-glycidoxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition.

[0057] The antistatic adhesive composition was coated on a release film using a doctor blade to form a coating film, and then the coating film was irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 25 mW for 60 seconds to perform a first-stage photocuring reaction, and then irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 55 mW for 60 seconds to perform a second-stage photocuring reaction, so that the coating film was converted into an optically transparent antistatic adhesive layer. The thickness of the antistatic adhesive layer was 250 μm, and the antistatic adhesive layer comprised an acrylate polymer having a carboxylic acid and 4-(dimethylamino)pyridine, and the 4-(dimethylamino)pyridine was ionically bonded to the carboxylic acid of the acidic acrylic acid segment of the acrylate polymer having a carboxylic acid.

[0058] Examples 2 to 15 and Comparative Examples 1 to 3

[0059] ​​Examples 2 to 15 and Comparative Examples 1 to 3 were carried out using the same steps as Example 1, with the main difference being that the types and amounts of each component were changed, and the process parameters were changed, as shown in Tables 2 to 5.

[0060] Comparative Example 4

[0061] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 2.69 parts by weight of the antistatic agent [Brand: Xinsheng International Co., Ltd.; Model: LQ-1107; CAS No. 405514-94-5; containing tributylmethylammonium bis(trifluoromethanesulfonyl)imide], 0.103 parts by weight of ethoxy(20)trimethylpropane triacrylate, and 0.08 parts by weight of 1-hydroxycyclohexylphenyl ketone (Brand: IGM Resins, Netherlands; Model: LQ-1107). 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (Brand: IGM Resins, Netherlands; Model: An antistatic adhesive composition was obtained by mixing 651) and 0.1 parts by weight of (3-epoxypropoxypropyl)trimethoxysilane (brand: Shin-Etsu Chemical Industry Co., Ltd.; model: KBM403).

[0062] Using a doctor blade, the antistatic adhesive composition is coated onto a release film to form a coating. Then, the coating is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 15 mW for 60 seconds for a first-stage photocuring reaction. Following this, it is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 35 mW for 60 seconds for a second-stage photocuring reaction, transforming the coating into an optically transparent antistatic adhesive layer. The thickness of this antistatic adhesive layer is 250 μm.

[0063] Comparative Example 5

[0064] Step (a): Mix 100 parts by weight of the first mixture of Preparation Example 1 and 1.34 parts by weight of the antistatic agent {Brand: KJ Chemicals Corporation; Model: DMAPAA} TM -Q; Contains water and 75 wt% N-[3-(dimethylamino)propyl]acrylamide, methylchloride quaternary), 0.106 parts by weight of ethoxy(20)trimethylpropane triacrylate, and 0.08 parts by weight of 1-hydroxycyclohexylphenyl ketone (Brand: IGM Resins, Netherlands; Model: 184) 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; type: IGM-UV 184) 651) 0.46 parts by weight of pentaerythritol tetra(3-mercaptopropionate) (brand: Evans Chemetics; type: Epi-Cure® 651) UV440-1) and 0.1 parts by weight of (3-glycidoxypropyl)trimethoxysilane (brand: Gelest; type: KBM 403) were mixed to obtain an antistatic adhesive composition.

[0065] The antistatic adhesive composition was coated on a release film using a doctor blade to form a coating film, and then the coating film was irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 15 mW for 60 seconds to perform a first-stage photocuring reaction, and then irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 35 mW for 60 seconds to perform a second-stage photocuring reaction, so that the coating film was converted into an optically transparent antistatic adhesive layer. The thickness of the antistatic adhesive layer was 250 μm.

[0066] Comparative Example 6

[0067] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 1.34 parts by weight of an antistatic agent (brand: KJ Chemicals Corporation; type: DMAEA TM -BQ; containing water and 75 wt% of dimethylaminoethyl acrylate, benzyl chloride quaternary), 0.106 parts by weight of ethoxylated (20) trimethylpropane triacrylate, 0.08 parts by weight of 1-hydroxycyclohexyl phenyl ketone (brand: IGM Resins, Netherlands; type: IGM-UV 6976) 184) 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; type: IGM-UV 184) 651) 0.46 parts by weight of pentaerythritol tetra(3-mercaptopropionate) (brand: Evanschemetics; type: Epi-Cure® 651) UV440-1) and 0.1 parts by weight of (3-glycidoxypropyl)trimethoxysilane (brand: Gelest; type: KBM 403) were mixed to obtain an antistatic adhesive composition.

[0068] Using a doctor blade, the antistatic adhesive composition is coated onto a release film to form a coating. Then, the coating is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 15 mW for 60 seconds for a first-stage photocuring reaction. Following this, it is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 35 mW for 60 seconds for a second-stage photocuring reaction, transforming the coating into an optically transparent antistatic adhesive layer. The thickness of this antistatic adhesive layer is 250 μm.

[0069] Comparative Example 7

[0070] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 1.402 parts by weight of acrylic acid, 1.598 parts by weight of imidazole, 0.106 parts by weight of ethoxy(20)trimethylpropane triacrylate, and 0.22 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model: 651), 0.46 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester (Brand: Evans Chemetics; Model: An antistatic adhesive composition is obtained by mixing UV440-1 and 0.1 parts by weight of (3-epoxypropoxypropyl)trimethoxysilane (brand: Shin-Etsu Chemical Industry Co., Ltd.; model: KBM403).

[0071] Using a doctor blade, the antistatic adhesive composition is coated onto a release film to form a coating. The coating is then irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 15 mW for 60 seconds as a first-stage photocuring reaction. Following this, it is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 35 mW for 60 seconds as a second-stage photocuring reaction, transforming the coating into an optically transparent antistatic adhesive layer. The thickness of this antistatic adhesive layer is 250 μm.

[0072] Comparative Example 8

[0073] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 0.456 parts by weight of acrylic acid, 0.944 parts by weight of triethylamine, 0.1 parts by weight of ethoxy(20)trimethylpropane triacrylate, and 0.08 parts by weight of 1-hydroxycyclohexylphenyl ketone (brand: IGM Resins, Netherlands; model: 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (Brand: IGM Resins, Netherlands; Model: An antistatic adhesive composition was obtained by mixing 651) and 0.1 parts by weight of (3-epoxypropoxypropyl)trimethoxysilane (brand: Shin-Etsu Chemical Industry Co., Ltd.; model: KBM403).

[0074] Using a doctor blade, the antistatic adhesive composition is coated onto a release film to form a coating. Then, the coating is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 15 mW for 60 seconds for a first-stage photocuring reaction. Following this, it is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 35 mW for 60 seconds for a second-stage photocuring reaction, transforming the coating into an optically transparent antistatic adhesive layer. The thickness of this antistatic adhesive layer is 250 μm.

[0075] Comparative Example 9

[0076] Step (a): 100 parts by weight of the first mixture of Preparation Example 1, 1.559 parts by weight of acrylic acid, 2.641 parts by weight of 4-(dimethylamino)pyridine, 0.103 parts by weight of ethoxy(20)trimethylpropane triacrylate, and 0.08 parts by weight of 1-hydroxycyclohexylphenyl ketone (brand: IGM Resins, Netherlands; model: 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (Brand: IGM Resins, Netherlands; Model: An antistatic adhesive composition was obtained by mixing 651) and 0.1 parts by weight of (3-epoxypropoxypropyl)trimethoxysilane (brand: Shin-Etsu Chemical Industry Co., Ltd.; model: KBM403).

[0077] Step (b): Using a doctor blade, the antistatic adhesive composition is coated onto a release film to form a coating. Then, the coating is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 25 mW for 60 seconds for a first-stage photocuring reaction. Next, it is irradiated with ultraviolet light at a wavelength of 365 nm and an exposure energy of 55 mW for 60 seconds for a second-stage photocuring reaction, transforming the coating into an optically transparent antistatic adhesive layer. The thickness of this antistatic adhesive layer is 250 μm, and it comprises an acrylate polymer containing a carboxylic acid and 4-(dimethylamino)pyridine, wherein the 4-(dimethylamino)pyridine is ionicly bonded to the carboxylic acid of the acidic acrylic segment of the acrylate polymer containing the carboxylic acid.

[0078] Comparative Example 10

[0079] Step (a): Mix 100 parts by weight of the first mixture of Preparation Example 1, 0.186 parts by weight of acrylic acid, and 1.34 parts by weight of antistatic agent {Brand: KJ Chemicals Corporation; Model: DMAPAA} TMQ; comprising water and 75 wt% of N-[3-(dimethylamino)propyl]acrylamide, methyl chloride quaternary), 0.103 parts by weight of ethoxylated (20) trimethylpropane triacrylate, 0.08 parts by weight of 1-hydroxycyclohexyl phenyl ketone (brand: IGM Resins, Netherlands; model number: IGM 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model number: IGM 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition. 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model number: IGM 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition. 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition.

[0080] Step (b): The antistatic adhesive composition was coated on a release film using a doctor blade to form a coating film, and then the coating film was irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 25 mW for 60 seconds to perform a first-stage photocuring reaction, and then irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 55 mW for 60 seconds to perform a second-stage photocuring reaction, so that the coating film was converted into an optically transparent antistatic adhesive layer. The thickness of the antistatic adhesive layer was 250 μm.

[0081] Comparative Example 11

[0082] Step (a): 100 parts by weight of the second mixture of Preparation Example 4, 1.32 parts by weight of (2,2'-diaminodiethyl)amine, 1.34 parts by weight of an antistatic agent {brand: KJ Chemicals Corporation; model number: DMAPAA TM Q; comprising water and 75 wt% of N-[3-(dimethylamino)propyl]acrylamide, methyl chloride quaternary), 0.103 parts by weight of ethoxylated (20) trimethylpropane triacrylate, 0.08 parts by weight of 1-hydroxycyclohexyl phenyl ketone (brand: IGM Resins, Netherlands; model number: IGM 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model number: IGM 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition. 184), 0.08 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (brand: IGM Resins, Netherlands; model number: IGM 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition. 651), and 0.1 parts by weight of (3-glycidyloxypropyl)trimethoxysilane (brand: Gelest; model number: KBM 403) were mixed to obtain an antistatic adhesive composition.

[0083] Step (b): The antistatic adhesive composition was coated on a release film using a doctor blade to form a coated film, and then the coated film was irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 25 mW for 60 seconds for a first-stage photocuring reaction, and then irradiated with ultraviolet light having a wavelength of 365 nm and an exposure energy of 55 mW for 60 seconds for a second-stage photocuring reaction, so that the coated film was converted into an optically transparent antistatic adhesive layer. The thickness of the antistatic adhesive layer was 250 μm.

[0084] Evaluation items

[0085] Surface resistance (unit: Ω / Dot) measurement: The antistatic adhesive layers of Examples 1 to 15 and Comparative Examples 1 to 11 were measured in accordance with the Insulating Materials - Direct Current Resistance or Conductance - Test Method, ASTM D257 (2021), using a high impedance meter (brand: Mitsubishi; model: MCPHT800) at a voltage of 500 V.

[0086] Heat resistance measurement: The antistatic adhesive layers of Examples 1 to 15 and Comparative Examples 1 to 11, each having a length of 60 mm and a width of 60 mm, were disposed between two polycarbonate sheets (thickness: 375 μm) each having a length of 80 mm and a width of 80 mm to obtain a laminate. The laminate was placed in a constant temperature oven set at 80°C for 1 hour, and then the laminate was taken out of the oven and cooled, and then the appearance of the laminate was visually observed for the presence of bubbles. The evaluation criteria were as follows.

[0087] A: No bubbles;

[0088] B: Peeling due to bubbles, and the number of bubbles was 1 to 5, and the diameter of the bubbles was less than 0.5 mm;

[0089] C: Peeling due to bubbles, and the number of bubbles was 6 to 10, and the diameter of the bubbles was less than 0.5 mm;

[0090] D: Peeling due to bubbles, and the number of bubbles was more than 1, and the diameter of the bubbles was 0.5 to 2 mm; and

[0091] E: Peeling due to bubbles, and the number of bubbles was more than 1, and the diameter of the bubbles was more than 0.5 mm.

[0092] Table 2

[0093]

[0094]

[0095]

[0096] Table 3

[0097]

[0098]

[0099] Table 4

[0100]

[0101]

[0102]

[0103] Table 5

[0104]

[0105]

[0106] Table 6

[0107]

[0108]

[0109] Table 7

[0110]

[0111]

[0112] Referring to Tables 2 to 4, in Examples 1 to 15, the organic nitrogen base (B) having two or more reactive nitrogens was used with the acidic (meth)acryloyloxy compound (a-3), and the total amount of the organic nitrogen base having two or more reactive nitrogens and the acidic (meth)acryloyloxy compound (a-3) was 0.4 parts by weight to 4 parts by weight (based on 100 parts by weight of the total amount of the composition), so that the antistatic adhesive layer was not easily separated from the polycarbonate sheet at the bonded portion of the antistatic adhesive layer and the polycarbonate sheet due to the blister phenomenon, and thus the antistatic adhesive layer of Examples 1 to 15 had good heat resistance.

[0113] Referring to Table 5, in Comparative Example 3, the total amount of the organic nitrogen base (B) having two or more reactive nitrogens and the acidic (meth)acryloyloxy compound (a-3) was 0.3 parts by weight (based on 100 parts by weight of the total amount of the composition), so that the antistatic adhesive layer was easily separated from the polycarbonate sheet at the bonded portion of the antistatic adhesive layer and the polycarbonate sheet due to the blister phenomenon, and thus the antistatic adhesive layer of Comparative Example 3 had poor heat resistance.

[0114] Referring to Tables 5 and 6, in Comparative Examples 4 to 6, the organic nitrogen base (B) having two or more reactive nitrogens was not used with the acidic (meth) acryloyloxy compound (a-3), and an ionic antistatic agent was used, causing the antistatic adhesive layer to easily separate from the polycarbonate sheet at the bonded portion of the antistatic adhesive layer and the polycarbonate sheet due to the occurrence of bubbles, and thus the heat resistance of the antistatic adhesive layer of Comparative Examples 4 to 6 was not good.

[0115] Referring to Table 6, in Comparative Examples 7 to 8, the organic nitrogen base (B) having two or more reactive nitrogens was not used, and an imidazole having only one reactive nitrogen capable of reacting with a carboxylic acid and triethylamine were used, causing the antistatic adhesive layer to easily separate from the polycarbonate sheet at the bonded portion of the antistatic adhesive layer and the polycarbonate sheet due to the occurrence of bubbles, and thus the heat resistance of the antistatic adhesive layer of Comparative Examples 7 to 8 was not good.

[0116] Referring to Table 7, in Comparative Example 9, the total amount of the organic nitrogen base (B) having two or more reactive nitrogens and the acidic (meth) acryloyloxy compound (a-3) was 4.2 parts by weight (based on 100 parts by weight of the total amount of the composition), causing the antistatic adhesive layer to easily separate from the polycarbonate sheet at the bonded portion of the antistatic adhesive layer and the polycarbonate sheet due to the occurrence of bubbles, and thus the heat resistance of the antistatic adhesive layer of Comparative Example 9 was not good.

[0117] In summary, by the combination of the types and amounts of the above components, especially the reaction of the organic nitrogen base (B) having two or more reactive nitrogens with the carboxylic acid of the (meth) acrylate polymer (A) having a carboxylic acid, the antistatic adhesive cured product not only has a low surface resistance, but also the product formed by the antistatic adhesive cured product being attached to an adherend (for example, a polycarbonate sheet) does not easily separate from the adherend at the bonded portion of the antistatic adhesive cured product and the adherend under high temperature (for example, 80°C or higher) conditions, causing the antistatic adhesive cured product to be firmly attached to the adherend, and thus the heat resistance of the antistatic adhesive cured product is good, and thus the purpose of the present application is achieved.

Claims

1. An antistatic adhesive cured product, characterized by comprising: a (meth)acrylate polymer (A) having a carboxylic acid, which is formed by a polymerization reaction of reaction components including a composition, a crosslinking agent (a-4) having two or more (meth)acrylate functional groups, and a photoinitiator (a-5), the composition including 54 to 90 wt% of a (meth)acrylate ester (a-1), 10 to 45 wt% of a non-acidic hydrophilic vinylic compound (a-2), and an acidic (meth)acryloyloxy compound (a-3), and, based on 100 parts by weight of the total amount of the composition, the crosslinking agent (a-4) having two or more (meth)acrylate functional groups is used in an amount of 0.05 to 2 parts by weight, and the photoinitiator (a-5) is used in an amount of 1 part by weight or less; an organic nitrogen base (B) having two or more reactive nitrogens, the reactive nitrogens of the organic nitrogen base (B) having two or more reactive nitrogens are ionically bonded to the carboxylic acid of the (meth)acrylate polymer (A) having a carboxylic acid, and, based on 100 parts by weight of the total amount of the composition, the total amount of the organic nitrogen base (B) having two or more reactive nitrogens and the acidic (meth)acryloyloxy compound (a-3) is 0.4 to 4 parts by weight.

2. The anti-static adhesive cured product according to claim 1, characterized by: The molar ratio of the organic nitrogen base (B) having two or more reactive nitrogens to the acidic (meth)acryloyloxy compound (a-3) is 1:3 to 3:

1.

3. The anti-static adhesive cured product according to claim 1, characterized by: The organic nitrogen base (B) having two or more reactive nitrogens is selected from 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2.2.2]octane, 1-(2-aminoethyl)piperazine, (2,2'-diaminodiethyl)amine, or a combination of any of the foregoing.

4. The anti-static adhesive cured product according to claim 1, characterized by: The acidic (meth)acryloyloxy compound (a-3) is selected from (meth)acrylic acid, a (meth)acrylate ester having a carboxylic acid, or a combination of the foregoing.

5. The anti-static adhesive cured product according to claim 1, characterized by: The non-acidic hydrophilic vinylic compound (a-2) is selected from a (meth)acrylate ester having a hydroxyl group, an acrylamide-based compound, an N-vinylamide-based compound, or a (meth)acrylate ester having an ether group, or a combination of the foregoing. The reaction components further include a silane coupling agent (a-7).

6. The anti-static adhesive cured product according to claim 1, characterized by: The content of the silane coupling agent (a-7) is 0.1 to 1 parts by weight, based on 100 parts by weight of the total amount of the composition.

7. The anti-static adhesive cured product according to claim 6, characterized by: The reaction components further include a chain transfer agent (a-6).

8. The anti-static adhesive cured product according to claim 1, characterized by: The content of the (meth)acrylate alkyl ester (a-1) is 54 to 85 wt%, based on 100 wt% of the total amount of the composition.

9. The anti-static adhesive cured product according to claim 1, characterized by: The content of the non-acidic hydrophilic vinylic compound (a-2) is 15 to 45 wt%, based on 100 wt% of the total amount of the composition.

10. The anti-static adhesive cured product according to claim 1, characterized by: ​

Images