A negative photosensitive resin composition and its preparation method and a hardening film

Abstract

This invention belongs to the field of touch display panel technology. It provides a negative photosensitive resin composition, its preparation method, and a curing film. The negative photosensitive resin composition comprises the following components in parts by weight: 100 parts of alkali-soluble resin, 30-200 parts of a carbon-carbon double bond-containing composition, 6-15 parts of a polyhydroxy compound, 15-24 parts of a polycarboxyl compound, 5-20 parts of a photoinitiator, and 100-500 parts of an organic solvent. The negative photosensitive resin composition of this invention possesses both low haze and high transmittance. The curing film prepared from it can combine the performance of a protective layer and a haze layer, fusing the protective layer and haze layer in traditional touch display devices into a single material, simplifying the original preparation process and reducing production costs. Furthermore, the curing film of this invention can also be used to prepare touch display devices with superior display effects, meeting higher product requirements.

Description

Technical Field

[0001] This invention relates to the field of touch display panel technology, and more particularly to a negative photosensitive resin composition, its preparation method, and a curing film. Background Technology

[0002] In the manufacturing process of touch display panels, touch panels typically have a multi-layered structure, including a special reinforcement layer, multiple conductive layers, multiple insulating layers, and a protective layer. This multi-layered design creates a touch panel capable of human-computer interaction. With the continuous development and application of electronic devices, the requirements for touch panels are increasing, and the application scenarios for touch display devices are becoming more diverse. Therefore, improving the display effect of touch panels and making touch display devices suitable for more scenarios has become a key research focus. In recent years, in daily use, touch display devices are often used in bright outdoor environments or well-lit indoor environments. In these situations, the reflection of strong light on the display screen can severely affect the display effect. Therefore, in the manufacturing process of touch display panels, a haze layer is generally coated in the final step of the manufacturing process. This haze layer reduces the reflection of incident light and has high transmittance. Without affecting the display effect, it reduces reflected light from the screen, increasing the clarity and contrast of the touch display screen. This improvement in visual effect enhances the user experience and satisfaction to a certain extent.

[0003] However, the haze layer in touch display panels is usually achieved by spraying a layer of silica onto the touch panel after the protective layer is applied, thus creating the desired haze effect. This process requires the use of multiple layers of materials, making it complex and costly.

[0004] Therefore, there is an urgent need to provide a hardened film prepared from a negative photosensitive resin composition that combines low haze and high transmittance to replace the haze layer in existing touch display panels, thereby solving the problem of complex and costly preparation process of the haze layer in existing touch display panels. Summary of the Invention

[0005] In view of this, the present invention provides a negative photosensitive resin composition, a method for preparing the same, and a curing film, to solve the problem that the preparation process of the haze layer in existing touch display panels is complex and costly.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a negative photosensitive resin composition comprising the following components in parts by weight:

[0008] The composition comprises 100 parts of alkali-soluble resin, 30-200 parts of carbon-carbon double bond-containing composition, 6-15 parts of polyhydroxy compound, 15-24 parts of polycarboxyl compound, 5-20 parts of photoinitiator, and 100-500 parts of organic solvent.

[0009] Preferably, the alkali-soluble resin is prepared by polymerization reaction of methacrylic acid monomer and free radical initiator; the average molecular weight of the alkali-soluble resin is 150,000 to 400,000, and the molecular weight distribution index is 2.8 to 5.0.

[0010] Preferably, the mass ratio of the methacrylic acid monomer to the free radical initiator is 1:0.001 to 0.2.

[0011] Preferably, the methacrylic acid monomer includes two or more of methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, hexyl methacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, benzyl methacrylate, lauryl methacrylate, stearate methacrylate, and dicyclopentyl methacrylate; the free radical initiator includes one or more of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxide, tert-butyl peroxyvalerate, azobisisobutyronitrile, and azobisisoheptanenitrile.

[0012] Preferably, the polymerization reaction is carried out at a temperature of 50–100°C for 3–15 hours.

[0013] Preferably, the carbon-carbon double bond-containing composition is obtained by mixing monofunctional monomers, difunctional monomers, and polyfunctional monomers.

[0014] Preferably, the monofunctional monomer comprises one or more of methacrylic acid, hydroxyethyl methacrylate, dicyclopentenyl acrylate, ethoxyethoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, m-phenoxybenzyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, laurate methacrylate, stearate methacrylate, propoxy nonylphenol acrylate, isodecayl acrylate, isooctyl acrylate, benzyl methacrylate, and isobornyl methacrylate; the bifunctional monomer comprises tricyclodecanedimethyl methacrylate. The polyfunctional monomer comprises one or more of the following: alcohol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, bisphenol A diacrylate ethoxylate, and ethylene glycol dimethacrylate; the polyfunctional monomer comprises one or more of the following: pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate ethoxylate, trimethylolpropane triacrylate propoxylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, and pentaerythritol hexaacrylate.

[0015] Preferably, the mass ratio of the monofunctional monomer, difunctional monomer, and polyfunctional monomer is 40-70:10-40:5-15.

[0016] Preferably, the polyhydroxy compound includes tris(2-hydroxyethyl) isocyanurate, 4',6,7-trihydroxyisoflavones, 2,4,6-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxyacetophenone, 2',3',4'-trihydroxyacetophenone, 2,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzamide, 3,4,5-trihydroxyphenylhydrazine, and 2,3,4-trihydroxybenzamide. One or more of the following: acid, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, tetrahydroxypregnenolone, 2,2,5,5-tetra(hydroxymethyl)cyclopentanone, 2,3,4,4'-tetrahydroxydiphenylmethane, 1,4,5,8-tetrahydroxyanthraquinone, 2,2',3,3'-tetrahydroxy-1,1'-biphenyl, and 2,3',4,5',6-pentahydroxybiphenyl.

[0017] Preferably, the polycarboxylic compound includes one or more of the following: tris(2-carboxyethyl)isocyanurate, 1,3,5-pentanetricarboxylic acid, 3,4',5-biphenyltricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, pyrrole-2,3,5-tricarboxylic acid, 1-aminophenyl-3,4,5-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 1,3,5,7-adamantanetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and benzenepentacarboxylic acid.

[0018] Preferably, the photoinitiator comprises one or more of the following: 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propanone, 1,1'-(methylenedi-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, benzophenone, benzoylbenzoic acid, isopropylthioxanthone, biphenylyl dimethyl alcohol, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trichlorotriazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole.

[0019] Preferably, the organic solvent includes one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diacetone alcohol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, and methyl 3-methoxypropionate.

[0020] Preferably, the negative photosensitive resin composition further includes additives, which include one or more of leveling agents, stabilizers, crosslinking agents, sensitizers, curing agents, dispersants, adhesion promoters, and defoamers.

[0021] The present invention also provides a method for preparing a negative photosensitive resin composition, comprising the following steps:

[0022] The components are mixed to obtain a negative photosensitive resin composition.

[0023] The present invention also provides a hardened film obtained by curing the negative photosensitive resin composition prepared by the above-described method for preparing the negative photosensitive resin composition.

[0024] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] The negative photosensitive resin composition provided by this invention has a low degree of crosslinking during the photocuring stage and a large amount of gas release after primary curing. This causes small molecules to continuously escape to the film surface after primary curing, resulting in a rough and uneven surface and a hazy effect. Simultaneously, the hardened film obtained from the negative photosensitive resin composition of this invention exhibits good adhesion and reliability, meeting the application requirements of protective layer materials. Therefore, the hardened film obtained from the negative photosensitive resin composition of this invention can serve as both a protective layer and a hazy layer in the fabrication of touch display devices. In other words, the hardened film of this invention can fuse the original protective layer and hazy layer in touch display devices into a single material, simplifying the original manufacturing process and reducing production costs. Furthermore, the hardened film of this invention also has high transmittance, and its use as both a protective layer and a hazy layer in touch display devices can impart superior display effects. Detailed Implementation

[0026] This invention provides a negative photosensitive resin composition comprising the following components in parts by weight:

[0027] The composition comprises 100 parts of alkali-soluble resin, 30-200 parts of carbon-carbon double bond-containing composition, 6-15 parts of polyhydroxy compound, 15-24 parts of polycarboxyl compound, 5-20 parts of photoinitiator, and 100-500 parts of organic solvent.

[0028] In this invention, the carbon-carbon double bond-containing composition is preferably 40-150 parts, more preferably 60-100 parts, and even more preferably 90 parts; the polyhydroxy compound is preferably 8-13 parts, and even more preferably 9-10 parts; the polycarboxyl compound is preferably 16-22 parts, and even more preferably 18-20 parts; the photoinitiator is preferably 6-15 parts, more preferably 7-10 parts, and even more preferably 8 parts; and the organic solvent is preferably 200-450 parts, more preferably 250-350 parts, and even more preferably 300 parts.

[0029] In this invention, the alkali-soluble resin is prepared by polymerization reaction of methacrylic acid monomer and free radical initiator; the average molecular weight of the alkali-soluble resin is 150,000 to 400,000, preferably 200,000 to 350,000, more preferably 250,000 to 300,000; the molecular weight distribution index is 2.8 to 5.0, preferably 3.0 to 4.5, more preferably 3.5 to 4.0.

[0030] In this invention, the preferred step for preparing the alkali-soluble resin is to dissolve methacrylic acid monomer and free radical initiator in a second organic solvent and carry out a polymerization reaction under a nitrogen atmosphere to obtain the alkali-soluble resin.

[0031] In this invention, the second organic solvent includes one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

[0032] In this invention, the mass ratio of the methacrylic acid monomer, the free radical initiator, and the second organic solvent is preferably 1:0.001-0.2:1-5, more preferably 1:0.003-0.1:1.5-4, and even more preferably 1:0.01-0.05:2-3.

[0033] In this invention, the methacrylic acid monomer includes two or more of methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, hexyl methacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, benzyl methacrylate, lauryl methacrylate, stearate methacrylate, and dicyclopentyl methacrylate, preferably including two or more of methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, benzyl methacrylate, and dicyclopentyl methacrylate, more preferably including two or more of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, benzyl methacrylate, and dicyclopentyl methacrylate.

[0034] In this invention, the free radical initiator includes one or more of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxide, tert-butyl peroxyvalerate, azobisisobutyronitrile, and azobisisoheptanenitrile, preferably including tert-butyl peroxyvalerate and / or azobisisobutyronitrile.

[0035] In this invention, the temperature of the polymerization reaction is 50-100°C, preferably 60-80°C, and more preferably 70°C; the time of the polymerization reaction is 3-15 hours, preferably 5-10 hours, and more preferably 7 hours.

[0036] In this invention, the carbon-carbon double bond-containing composition is obtained by mixing monofunctional monomers, difunctional monomers and polyfunctional monomers.

[0037] In this invention, the monofunctional monomer includes one or more of the following: methacrylic acid, hydroxyethyl methacrylate, dicyclopentenyl acrylate, ethoxyethoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, m-phenoxybenzyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, laurate methacrylate, stearate methacrylate, propoxy nonylphenol acrylate, isodecyl acrylate, isooctyl acrylate, benzyl methacrylate, and isobornyl methacrylate.

[0038] In this invention, the bifunctional monomer includes one or more of tricyclodecanediethanol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, bisphenol A diacrylate ethoxylate, and ethylene glycol dimethacrylate.

[0039] In this invention, the polyfunctional monomer includes one or more of pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, and pentaerythritol hexaacrylate.

[0040] In this invention, the mass ratio of the monofunctional monomer, difunctional monomer, and polyfunctional monomer is 40-70:10-40:5-15, preferably 45-65:15-35:6-13, and more preferably 50-60:25-30:8-10.

[0041] In this invention, the polyhydroxy compounds include tris(2-hydroxyethyl) isocyanurate, 4',6,7-trihydroxyisoflavones, 2,4,6-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxyacetophenone, 2',3',4'-trihydroxyacetophenone, 2,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzamide, 3,4,5-trihydroxyphenylhydrazine, and 2,3,4-trihydroxybenzene. Formic acid, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, tetrahydroxypregnenolone, 2,2,5,5-tetra(hydroxymethyl)cyclopentanone, 2,3,4,4'-tetrahydroxydiphenylmethane, 1,4,5,8-tetrahydroxyanthraquinone, 2,2',3,3'-tetrahydroxy-1,1'-biphenyl, 2,3',4,5',6-pentahydroxybiphenyl, or one or more of these.

[0042] In this invention, the polycarboxylic acid compound includes one or more of the following: tris(2-carboxyethyl)isocyanurate, 1,3,5-pentanetricarboxylic acid, 3,4',5-biphenyltricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, pyrrole-2,3,5-tricarboxylic acid, 1-aminophenyl-3,4,5-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 1,3,5,7-adamantanetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and benzenepentacarboxylic acid.

[0043] In this invention, the mass ratio of the polyhydroxy compound to the polycarboxyl compound is preferably 1-2:0.5-1, more preferably 1.2-1.8:0.6-0.8, and even more preferably 1.5:0.7.

[0044] In this invention, the photoinitiator includes 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propanone, 1,1'-(methylenedi-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, and diphenyl One or more of methyl ketone, benzoylbenzoic acid, isopropylthioxanthone, biphenyl dimethyl acetal, 4-benzoyl-4'-methyl diphenyl sulfide, 2,4,6-trichlorotriazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, preferably including 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone and / or 2-isopropylthioxanthraphenone.

[0045] In this invention, the organic solvent includes one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diacetone alcohol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, and methyl 3-methoxypropionate, preferably including propylene glycol methyl ether acetate and / or propylene glycol methyl ether.

[0046] In this invention, the negative photosensitive resin composition further includes additives, which include one or more of leveling agents, stabilizers, crosslinking agents, sensitizers, curing agents, dispersants, adhesion promoters and defoamers, preferably including leveling agents and / or adhesion promoters, wherein the additives may be used alone or in combination as needed.

[0047] In this invention, based on 100 parts by weight of the alkali-soluble resin, the amount of leveling agent added is preferably 0.05 to 1 part, more preferably 0.06 to 0.08 parts, and even more preferably 0.07 parts; the leveling agent preferably includes fluorinated surfactants and / or silicone surfactants, wherein the fluorinated surfactant is preferably Shin-Etsu Chemical's KF-69, and the silicone surfactant is preferably Shin-Etsu Chemical's KP-341. The addition of the leveling agent helps to better coat the film layer and improve the uniformity and appearance quality of the film layer.

[0048] In this invention, based on 100 parts by weight of the alkali-soluble resin, the amount of the adhesion promoter added is preferably 1 to 15 parts, more preferably 2 to 10 parts, and even more preferably 3 to 8 parts; the adhesion promoter preferably includes one or more of (3-mercaptopropyl)trimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane, more preferably γ-glycidoxypropyltrimethoxysilane. The addition of the adhesion promoter can enhance the adhesion of the composition to the substrate.

[0049] The present invention also provides a method for preparing the above-mentioned negative photosensitive resin composition, comprising the following steps:

[0050] The components are mixed to obtain a negative photosensitive resin composition.

[0051] In this invention, the process of obtaining the negative photosensitive resin composition further includes a filtration operation.

[0052] The present invention also provides a hardened film obtained by curing the negative photosensitive resin composition prepared by the above-mentioned method.

[0053] In this invention, the method for preparing the hardened film includes the following steps:

[0054] 1) A negative photosensitive resin composition is coated onto a substrate to form a wet film;

[0055] 2) Dry the coated wet film to form a dry film;

[0056] 3) Expose the dry film;

[0057] 4) Develop the exposed dry film;

[0058] 5) Heat the developed dry film to obtain a hardened film.

[0059] In this invention, the substrate in step 1) preferably includes one of a soda-lime glass substrate, a borosilicate glass substrate, a PET substrate, and a metal substrate; the coating method preferably includes one of spin coating, roll coating, screen printing, spraying, slot coating, and transfer printing.

[0060] In this invention, the drying temperature in step 2) is preferably 80-130°C, more preferably 90-110°C, and even more preferably 100°C; the drying time is preferably 1-5 minutes, more preferably 2-4 minutes, and even more preferably 3 minutes.

[0061] In this invention, the light source for exposure in step 3) preferably includes a mercury lamp or an LED lamp (365nm); the light intensity for exposure is preferably 10-100 mJ / cm².2 Further preferred is 15–40 mJ / cm 2 More preferably 20 mJ / cm 2 .

[0062] In this invention, the developing solution in step 4) preferably includes one or more of potassium hydroxide, sodium hydroxide, sodium bicarbonate, tetramethylammonium hydroxide, potassium hydroxide / surfactant system, and sodium hydroxide / sodium bicarbonate / surfactant system, more preferably potassium hydroxide / surfactant system; the developing method preferably includes immersion and / or spraying.

[0063] In this invention, the heating temperature in step 5) is preferably 200-240°C, more preferably 220-235°C, and even more preferably 230°C; the heating time is preferably 25-50 minutes, more preferably 26-40 minutes, and even more preferably 30 minutes.

[0064] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0065] Example 1

[0066] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 2:6:5:4:3, 0.15 parts of azobisisobutyronitrile and 30 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C for 7 hours under a nitrogen atmosphere to obtain an alkali-soluble resin with an average molecular weight of 150,000 and a molecular weight distribution index of 2.8.

[0067] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 70:15:15 to obtain carbon-carbon double bond composition.

[0068] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 30 parts of carbon-carbon double bond composition, 6 parts of tris(2-hydroxyethyl) isocyanurate, 15 parts of tris(2-carboxyethyl) isocyanurate, 5 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 200 parts of propylene glycol methyl ether acetate, 0.05 parts of KP-341, and 2 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly, and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0069] Example 2

[0070] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 8:25:20:35:12, 0.16 parts of azobisisobutyronitrile and 35 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C for 7 hours under a nitrogen atmosphere to obtain an alkali-soluble resin with an average molecular weight of 200,000 and a molecular weight distribution index of 3.0.

[0071] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 60:25:15 to obtain carbon-carbon double bond composition.

[0072] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 40 parts of carbon-carbon double bond composition, 8 parts of tris(2-hydroxyethyl)isocyanurate, 16 parts of tris(2-carboxyethyl)isocyanurate, 6 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 250 parts of propylene glycol methyl ether acetate, 0.06 parts of KP-341, and 3 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly, and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0073] Example 3

[0074] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 2:4:3:5:6, 0.17 parts of azobisisobutyronitrile and 40 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C for 7 hours under a nitrogen atmosphere to obtain an alkali-soluble resin with an average molecular weight of 400,000 and a molecular weight distribution index of 5.0.

[0075] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 65:30:15 to obtain carbon-carbon double bond composition.

[0076] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 60 parts of carbon-carbon double bond composition, 15 parts of tris(2-hydroxyethyl)isocyanurate, 15 parts of tris(2-carboxyethyl)isocyanurate, 8 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 300 parts of propylene glycol methyl ether acetate, 0.07 parts of KP-341, and 4 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly, and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0077] Example 4

[0078] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 2:5:8:5:5, 0.2 parts of azobisisobutyronitrile and 50 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C for 7 hours under a nitrogen atmosphere to obtain an alkali-soluble resin with an average molecular weight of 350,000 and a molecular weight distribution index of 4.5.

[0079] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 50:40:10 to obtain carbon-carbon double bond composition.

[0080] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 90 parts of carbon-carbon double bond composition, 15 parts of tris(2-hydroxyethyl)isocyanurate, 24 parts of tris(2-carboxyethyl)isocyanurate, 10 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 350 parts of propylene glycol methyl ether acetate, 0.08 parts of KP-341, and 8 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly, and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0081] Example 5

[0082] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 2:7:7:2:2, 1 part of azobisisobutyronitrile and 70 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C under a nitrogen atmosphere for 7 hours to obtain an alkali-soluble resin with an average molecular weight of 250,000 and a molecular weight distribution index of 3.2.

[0083] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 45:40:15 to obtain carbon-carbon double bond composition.

[0084] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 200 parts of carbon-carbon double bond composition, 6 parts of tris(2-hydroxyethyl)isocyanurate, 24 parts of tris(2-carboxyethyl)isocyanurate, 20 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 450 parts of propylene glycol methyl ether acetate, 11 parts of KP-3411 parts and 14 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0085] Example 6

[0086] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, benzyl methacrylate and dicyclopentyl methacrylate in a mass ratio of 2:7:7:2:2, 1 part of azobisisobutyronitrile and 70 parts of propylene glycol methyl ether acetate were added to a four-necked flask and reacted at 70°C under a nitrogen atmosphere for 7 hours to obtain an alkali-soluble resin with an average molecular weight of 250,000 and a molecular weight distribution index of 3.2.

[0087] Preparation of carbon-carbon double bond composition: Hydroxyethyl methacrylate, dipropylene glycol diacrylate and pentaerythritol triacrylate are mixed in a mass ratio of 45:40:15 to obtain carbon-carbon double bond composition.

[0088] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 200 parts of carbon-carbon double bond composition, 6 parts of tris(2-hydroxyethyl) isocyanurate, 24 parts of tris(2-carboxyethyl) isocyanurate, 20 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, and 450 parts of propylene glycol methyl ether acetate were stirred evenly and filtered using a filtration device to obtain the negative photosensitive resin composition.

[0089] Application Example 1

[0090] The hardened film was prepared using the negative photosensitive resin composition obtained in Example 1, and the specific steps are as follows:

[0091] 1) The negative photosensitive resin composition is spin-coated onto a soda-lime glass substrate to form a wet film;

[0092] 2) Place the coated wet film in a vacuum drying equipment, maintain it under a pressure of 50 Pa for 10 seconds, and then use a hot plate to heat it to 100°C for 3 minutes to form a dry film;

[0093] 3) Expose the dry film using an exposure machine (mercury lamp as the light source), wherein the light intensity during the exposure process is 20 mJ / cm². 2 ;

[0094] 4) The exposed dry film is developed using a potassium hydroxide / surfactant system (KOH:surfactant:water = 0.06:0.3:99.1) developer by immersion.

[0095] 5) Place the developed dry film into an oven and heat it at 230°C for 30 minutes to obtain a hardened film.

[0096] Application Example 2

[0097] The hardened film was prepared using the same method as in Application Example 1. The only difference between Application Example 2 and Application Example 1 is that the negative photosensitive resin composition is the negative photosensitive resin composition prepared in Example 2.

[0098] Application Example 3

[0099] The hardened film was prepared using the same method as in Application Example 1. The only difference between Application Example 3 and Application Example 1 is that the negative photosensitive resin composition is the negative photosensitive resin composition prepared in Example 3.

[0100] Application Example 4

[0101] The hardened film was prepared using the same method as in Application Example 1. The only difference between Application Example 4 and Application Example 1 is that the negative photosensitive resin composition is the negative photosensitive resin composition prepared in Example 4.

[0102] Application Example 5

[0103] The hardened film was prepared using the same method as in Application Example 1. The only difference between Application Example 5 and Application Example 1 is that the negative photosensitive resin composition is the negative photosensitive resin composition prepared in Example 5.

[0104] Application Example 6

[0105] The hardened film was prepared using the same method as in Application Example 1. The only difference between Application Example 6 and Application Example 1 is that the negative photosensitive resin composition is the negative photosensitive resin composition prepared in Example 6.

[0106] Comparative Example 1

[0107] Alkali-soluble resin: Conventional acrylic resin with a molecular weight of 100,000 and a molecular weight distribution index of 2.5.

[0108] Preparation of negative photosensitive resin composition: 100 parts of alkali-soluble resin, 200 parts of pentaerythritol triacrylate, 5 parts of conventional photoinitiator 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 450 parts of propylene glycol methyl ether acetate, 11 parts of KP-3411 and 14 parts of γ-glycidyl etheroxypropyltrimethoxysilane were mixed, stirred evenly and filtered using a filter device to obtain the negative photosensitive resin composition.

[0109] Then, the negative photosensitive resin composition prepared in Comparative Example 1 was used to prepare a hardened film using the same hardened film preparation method as in Application Example 1.

[0110] The hardened films prepared for use cases 1 to 6 and comparative example 1 were subjected to routine performance tests, and the results are shown in Table 1.

[0111] Adhesion determination: The adhesion of the hardened film was tested using the cross-cut adhesion test. The adhesion evaluation grades from best to worst are: 5B, 4B, 3B, 2B, 1B, 0B.

[0112] Reliability testing: The hardened film is placed in a high-temperature and high-humidity test chamber for 500–1200 hours. The adhesion of the film layer is recorded at different times (every 100 hours). 3M tape is used to test the adhesion of the hardened film. The test ends when the hardened film layer peels off. The longer the time, the better the reliability. A reliability exceeding 1000 hours meets the application requirements of conventional protective layer materials.

[0113] Transmittance determination: The full-band transmittance data of the hardened film was tested using the UV-vis of Agilent Carry-3000, and the transmittance at a wavelength of 400nm was extracted.

[0114] Haze measurement: The haze value of the hardened film was tested using the UV-vis of the Agilent Carry-3000.

[0115] Table 1 Performance test results of the hardened film

[0116]

[0117] As shown in Table 1, the hardened films prepared in Application Examples 1-6 all exhibit good adhesion and reliability, meeting the application requirements of protective layer materials and can be used as protective layers in touch display devices. Furthermore, compared to Comparative Example 1, the hardened films obtained by this invention also possess high transmittance and a certain haze value, making them suitable as haze layers in touch display devices. Therefore, the hardened film of this invention can combine the performance of both a protective layer and a haze layer, fusing the original protective layer and haze layer in touch display devices into a single material, simplifying the original preparation process and reducing production costs. In addition, the hardened film of this invention can also be used to prepare touch display devices with superior display effects, meeting higher product requirements.

[0118] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A negative photosensitive resin composition, characterized in that, The components include the following parts by mass: 100 parts of alkali-soluble resin, 30-200 parts of carbon-carbon double bond composition, 6-15 parts of polyhydroxy compound, 15-24 parts of polycarboxyl compound, 5-20 parts of photoinitiator, and 100-500 parts of organic solvent; The carbon-carbon double bond-containing composition is obtained by mixing monofunctional monomers, difunctional monomers and polyfunctional monomers; The monofunctional monomer includes hydroxyethyl methacrylate; the difunctional monomer includes dipropylene glycol diacrylate. The polyfunctional monomer includes pentaerythritol triacrylate; The mass ratio of the monofunctional monomer, difunctional monomer, and polyfunctional monomer is 40~70:10~40:5~15; The polyhydroxy compound includes tris(2-hydroxyethyl) isocyanurate; the polycarboxylic compound includes tris(2-carboxyethyl) isocyanurate.

2. The negative photosensitive resin composition according to claim 1, characterized in that, The alkali-soluble resin is prepared by polymerization reaction of methacrylic acid monomer and free radical initiator; The alkali-soluble resin has an average molecular weight of 150,000 to 400,000 and a molecular weight distribution index of 2.8 to 5.

0.

3. The negative photosensitive resin composition according to claim 2, characterized in that, The mass ratio of the methacrylic acid monomer to the free radical initiator is 1:0.001~0.2; The methacrylic acid monomer includes two or more of the following: methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, hexyl methacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, benzyl methacrylate, lauryl methacrylate, stearate methacrylate, and dicyclopentyl methacrylate. The free radical initiator includes one or more of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxide, tert-butyl peroxyvalerate, azobisisobutyronitrile, and azobisisoheptanenitrile.

4. The negative photosensitive resin composition according to claim 3, characterized in that, The polymerization reaction is carried out at a temperature of 50~100℃ for 3~15h.

5. A negative photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The photoinitiator includes one or more of the following: 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propanone, 1,1'-(methylenedi-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthonone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, benzophenone, benzoylbenzoic acid, isopropylthioxanthone, biphenyl dimethyl alcohol, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trichlorotriazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole; The organic solvent includes one or more of the following: propylene glycol methyl ether acetate, propylene glycol methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diacetone alcohol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, and methyl 3-methoxypropionic acid.

6. The negative photosensitive resin composition according to claim 5, characterized in that, The negative photosensitive resin composition further includes additives, which include one or more of the following: leveling agents, stabilizers, crosslinking agents, sensitizers, curing agents, dispersants, adhesion promoters, and defoamers.

7. A method for preparing a negative photosensitive resin composition according to any one of claims 1 to 6, characterized in that, Includes the following steps: The components are mixed to obtain a negative photosensitive resin composition.

8. A hardened film, characterized in that, The negative photosensitive resin composition prepared by the method of claim 7 is obtained by curing.

Images