Negative photosensitive resin composition, preparation method thereof and hardened film

Abstract

The invention belongs to the technical field of touch display panels, and provides a negative photosensitive resin composition, a preparation method thereof and a hardened film. The negative photosensitive resin composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin, 30-200 parts of a composition containing carbon-carbon double bonds, 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 has both low haze and high permeability, a hardened film prepared from the negative photosensitive resin composition can have both the performance of a protective layer and the performance of a haze layer, the protective layer and the haze layer in an original touch display device are fused into one layer of material, the original preparation process is simplified, and the production cost is reduced. Meanwhile, the hard coating film can be used for preparing a touch display device with a more excellent display effect, and higher product requirements can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of touch display panels, and in particular to a negative photosensitive resin composition and a preparation method thereof and a hardened film. Background Art

[0002] In the process of preparing a touch display panel, the touch panel usually has a multi-layer structure, including a special reinforcement layer, a multi-layer conductive layer, a multi-layer insulating layer and a protective layer. This multi-layer structure design can form a touch panel that can realize human-computer interaction. With the continuous development and application of electronic devices, the requirements for touch panels are increasing, and the application scenarios of touch display devices are becoming more and more diverse. Therefore, how to improve the display effect of touch panels and make touch display devices suitable for more scenarios has become the focus of people's research. In recent years, in the daily use of touch display devices, touch devices are usually used in brighter outdoor or well-lit indoor environments. In this case, the reflection of strong light in the display screen will seriously affect the display effect of the touch device. Therefore, in the process of preparing a touch display panel, a haze layer is generally applied in the last step of its preparation process. The haze layer can reduce the reflection of incident light and has high transmittance. While not affecting the display effect, it reduces the reflected light of the screen and increases the clarity and contrast of the touch display screen. This improvement in visual effects has improved the user experience and satisfaction to a certain extent.

[0003] However, the haze layer in the touch display panel is usually sprayed with a layer of silicon dioxide after the touch panel is completed with a protective layer, so as to achieve the corresponding haze effect. This process requires the use of multiple layers of materials, the process is complex and the cost is high.

[0004] Therefore, there is an urgent need to provide a hardened film prepared from a negative photosensitive resin composition with low haze and high transmittance to replace the haze layer in the existing touch display panel and solve the problem of complex preparation process and high cost of the haze layer in the existing touch display panel. Summary of the invention

[0005] In view of this, the present invention provides a negative photosensitive resin composition and a preparation method thereof and a hardened film to solve the problem that the preparation process of the haze layer in the existing touch display panel is complicated and the cost is high.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

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

[0008] 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 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 1:0.001-0.2.

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

[0012] Preferably, the polymerization reaction temperature is 50-100° C. and the time is 3-15 hours.

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

[0014] Preferably, the monofunctional monomer includes one or more of methacrylic acid, hydroxyethyl methacrylate, dicyclopentenyl acrylate, ethoxyethoxyethyl acrylate, 4-tert-butyl cyclohexyl acrylate, m-phenoxybenzyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, methacrylate laurate, methacrylate stearate, propoxylated nonylphenol acrylate, isodecyl acrylate, isooctyl acrylate, benzyl methacrylate and isobornyl methacrylate; the difunctional monomer includes tricyclodecane dimethyl acrylate, The polyfunctional monomer comprises one or more of pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate and pentaerythritol hexaacrylate.

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

[0016] Preferably, the polyol comprises tris(2-hydroxyethyl)isocyanurate, 4',6,7-trihydroxyisoflavone, 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, 2,3,4-trihydroxybenzaldehyde, One or more of acid, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, tetrahydroxypregnenolone, 2,2,5,5-tetrakis(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 polycarboxyl compound includes one or more of 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-aminobenzene-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 includes 1-hydroxycyclohexyl phenyl 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-morpholinyl-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, dibenzophenone, benzoylbenzoic acid, isopropylthioxanthone, benzyl dimethyl acetal, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trichloro-s-triazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetrakis(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 comprises additives, and the additives include one or more of a leveling agent, a stabilizer, a cross-linking agent, a sensitizer, a curing agent, a dispersant, an adhesion aid and a defoaming agent.

[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 hardening the negative photosensitive resin composition prepared by the method for preparing the negative photosensitive resin composition.

[0024] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0025] The negative photosensitive resin composition provided by the present invention has a low degree of crosslinking in the photocuring stage, and a large amount of outgassing after the main curing, so that the film layer continuously releases small molecules to the surface of the film layer after the main curing, so that the surface of the film layer after the main curing appears rough and uneven, producing a haze effect. At the same time, the hardened film obtained from the negative photosensitive resin composition of the present invention has good adhesion and reliability, and can meet the application requirements of the protective layer material. Therefore, the hardened film obtained from the negative photosensitive resin composition provided by the present invention can be used as a protective layer in the preparation of a touch display device, and can also be used as a haze layer in the preparation of a touch display device. That is, the hardened film of the present invention can fuse the protective layer and the haze layer in the original touch display device into a layer of material, simplifying the original preparation process and reducing production costs. In addition, the hardened film of the present invention also has a high transmittance, and its use as a protective layer and a haze layer in a touch display device can give the touch display device a better display effect. DETAILED DESCRIPTION

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

[0027] 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 the present invention, the carbon-carbon double bond-containing composition is preferably 40 to 150 parts, more preferably 60 to 100 parts, and more preferably 90 parts; the polyhydroxy compound is preferably 8 to 13 parts, more preferably 9 to 10 parts; the polycarboxyl compound is preferably 16 to 22 parts, more preferably 18 to 20 parts; the photoinitiator is preferably 6 to 15 parts, more preferably 7 to 10 parts, and more preferably 8 parts; the organic solvent is preferably 200 to 450 parts, more preferably 250 to 350 parts, and more preferably 300 parts.

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

[0030] In the present invention, the step of preparing the alkali-soluble resin is preferably: dissolving methacrylic acid monomer and free radical initiator in a second organic solvent, and performing polymerization reaction under a nitrogen atmosphere to obtain the alkali-soluble resin.

[0031] In the present 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 the present 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 more preferably 1:0.01-0.05:2-3.

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

[0034] In the present invention, the free radical initiator includes one or more of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl perbenzoate, tert-butyl perpentylate, azobisisobutyronitrile and azobisisoheptylonitrile, preferably tert-butyl perpentylate and / or azobisisobutyronitrile.

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

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

[0037] In the present invention, the monofunctional monomer includes one or more of methacrylic acid, hydroxyethyl methacrylate, dicyclopentenyl acrylate, ethoxyethoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, m-phenoxybenzyl acrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, lauric methacrylate, stearic methacrylate, propoxylated nonylphenol acrylate, isodecyl acrylate, isooctyl acrylate, benzyl methacrylate and isobornyl methacrylate.

[0038] In the present invention, the difunctional monomer includes one or more of tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, ethoxylated bisphenol A diacrylate and ethylene glycol dimethacrylate.

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

[0040] In the present invention, the mass ratio of the monofunctional monomer, the difunctional monomer and the 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 the present invention, the polyhydroxy compound includes tris (2-hydroxyethyl) isocyanurate, 4',6,7-trihydroxy isoflavone, 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, 2,3,4-trihydroxybenzene One or more of formic acid, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, tetrahydroxypregnenolone, 2,2,5,5-tetrakis(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.

[0042] In the present invention, the polycarboxyl compound includes one or more of 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-aminobenzene-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 the present 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 the present invention, the photoinitiator includes 1-hydroxycyclohexyl phenyl 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-morpholinyl-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, diphenyl One or more of ketone, benzoylbenzoic acid, isopropylthioxanthone, benzyl dimethyl acetal, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trichloro-s-triazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, preferably including 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone and / or 2-isopropylthioxanthone.

[0045] In the present 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 the present invention, the negative photosensitive resin composition also includes additives, and the additives include one or more of a leveling agent, a stabilizer, a cross-linking agent, a sensitizer, a curing agent, a dispersant, an adhesion aid and a defoaming agent, preferably including a leveling agent and / or an adhesion aid, wherein the additives can be used alone or in combination according to needs.

[0047] In the present invention, based on 100 parts by mass of the alkali-soluble resin, the added amount of the leveling agent is preferably 0.05 to 1 part, more preferably 0.06 to 0.08 part, and more preferably 0.07 part; the leveling agent preferably includes a fluorine-based surfactant and / or a silicon-based surfactant, wherein the fluorine-based surfactant is preferably KF-69 of Shin-Etsu Chemical, and the silicon-based surfactant is preferably KP-341 of Shin-Etsu Chemical. 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 the present invention, based on 100 parts by mass of the alkali-soluble resin, the added amount of the adhesion aid is preferably 1 to 15 parts, further preferably 2 to 10 parts, and more preferably 3 to 8 parts; the adhesion aid preferably includes one or more of (3-mercaptopropyl)trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, more preferably γ-glycidyloxypropyltrimethoxysilane. The addition of the adhesion aid can enhance the connectivity of the composition to the substrate.

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

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

[0051] In the present invention, the process of obtaining the negative photosensitive resin composition further includes filtering.

[0052] The present invention also provides a hardened film obtained by hardening the negative photosensitive resin composition prepared by the method for preparing the negative photosensitive resin composition.

[0053] In the present invention, the method for preparing the hardened film comprises the following steps:

[0054] 1) coating a negative photosensitive resin composition on a substrate to form a coating wet film;

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

[0056] 3) exposing the dry film;

[0057] 4) developing the exposed dry film;

[0058] 5) The developed dry film is heated to obtain a hardened film.

[0059] In the present invention, the substrate in step 1) preferably includes one of a soda-lime glass substrate, a high borosilicate substrate, a PET substrate and a metal substrate; the coating method preferably includes one of spin coating, roller coating, screen printing, spray coating, slit coating and transfer.

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

[0061] In the present invention, the light source for exposure in step 3) preferably includes a mercury lamp or an LED lamp (365 nm); the light product of the exposure is preferably 10 to 100 mJ / cm2 , more preferably 15 to 40 mJ / cm 2 , more preferably 20 mJ / cm 2 .

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

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

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

[0065] Example 1

[0066] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 for 7 hours under a nitrogen atmosphere at a temperature of 70°C 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 the 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 a carbon-carbon double bond composition.

[0068] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 30 parts of a 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-morpholinyl-1-propanone, 200 parts of propylene glycol methyl ether acetate, 0.05 parts of KP-341 and 2 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0069] Example 2

[0070] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 under a nitrogen atmosphere at a temperature of 70°C for 7 hours 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 the 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 a carbon-carbon double bond composition.

[0072] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 40 parts of a 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-morpholinyl-1-propanone, 250 parts of propylene glycol methyl ether acetate, 0.06 parts of KP-341 and 3 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0073] Example 3

[0074] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 under a nitrogen atmosphere at a temperature of 70°C for 7 hours 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 the 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 a carbon-carbon double bond composition.

[0076] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 60 parts of a 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-morpholinyl-1-propanone, 300 parts of propylene glycol methyl ether acetate, 10.07 parts of KP-341 and 4 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0077] Example 4

[0078] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 under a nitrogen atmosphere at a temperature of 70°C for 7 hours 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 the 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 a carbon-carbon double bond composition.

[0080] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 90 parts of a 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-morpholinyl-1-propanone, 350 parts of propylene glycol methyl ether acetate, 10.08 parts of KP-341 and 8 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0081] Example 5

[0082] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 are added to a four-necked flask, and reacted under a nitrogen atmosphere at a temperature of 70°C 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 the 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 a carbon-carbon double bond composition.

[0084] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 200 parts of a 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-morpholinyl-1-propanone, 450 parts of propylene glycol methyl ether acetate, 11 parts of KP-34 and 14 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0085] Example 6

[0086] Preparation of alkali-soluble resin: 15 parts of a mixture of methacrylic acid, hydroxyethyl methacrylate, 3-(isobutyleneoxy)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 are added to a four-necked flask, and reacted under a nitrogen atmosphere at a temperature of 70°C 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 the 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 a carbon-carbon double bond composition.

[0088] Preparation of a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 200 parts of a 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-morpholinyl-1-propanone, and 450 parts of propylene glycol methyl ether acetate are stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0089] Application Example 1

[0090] The negative photosensitive resin composition prepared in Example 1 is used to prepare a hardened film, and the specific steps are as follows:

[0091] 1) applying a negative photosensitive resin composition on a soda-lime glass substrate by spin coating to form a coating wet film;

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

[0093] 3) Use an exposure machine (the light source is a mercury lamp) to expose the dry film, where the light volume of the exposure process is 20mJ / cm 2 ;

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

[0095] 5) The developed dry film was placed in an oven and heated at 230° C. for 30 minutes to obtain a hardened film.

[0096] Application Example 2

[0097] The cured film was prepared by the same cured film preparation method as that of Application Example 1, wherein the 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 cured film was prepared by the same cured film preparation method as that of Application Example 1, wherein the 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 cured film was prepared by the same cured film preparation method as that of Application Example 1, wherein the 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 cured film was prepared by the same cured film preparation method as that of Application Example 1, wherein the 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 cured film was prepared by the same cured film preparation method as that of Application Example 1, wherein the difference between Application Example 6 and Application Example 1 is only 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 a negative photosensitive resin composition: 100 parts of an alkali-soluble resin, 200 parts of pentaerythritol triacrylate, 5 parts of a conventional photoinitiator 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 450 parts of propylene glycol methyl ether acetate, 11 parts of KP-34 and 14 parts of γ-glycidyloxypropyltrimethoxysilane are mixed, stirred evenly and filtered using a filtering device to obtain a negative photosensitive resin composition.

[0109] Then, the negative photosensitive resin composition prepared in this comparative example 1 was used and a hardened film was prepared by the same hardened film preparation method as in application example 1.

[0110] Conventional performance tests were performed on the hardened films prepared in Examples 1 to 6 and Comparative Example 1. The results are shown in Table 1.

[0111] Adhesion test: The adhesion of the hardened film was tested using the 100-grid test method. The order of adhesion evaluation from good to bad is: 5B, 4B, 3B, 2B, 1B, 0B.

[0112] Determination of reliability: Place the hardened film in a high temperature and high humidity test chamber for 500 to 1200 hours, record the adhesion of the film at different times (every 100 hours), use 3M tape to test the adhesion of the hardened film, and end the test when the hardened film falls off. Record the time the hardened film is placed. The longer the time, the better the reliability. Reliability of more than 1000 hours can meet the application requirements of conventional protective layer materials.

[0113] Transmittance measurement: Use Agilent Carry-3000 UV-vis to test the full-band transmittance data of the hardened film layer, and intercept the transmittance at a wavelength of 400nm.

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

[0115] Table 1 Performance test results of hardened film

[0116]

[0117] As shown in Table 1, the hardened films prepared in Application Examples 1 to 6 all have good adhesion and reliability, meet the application requirements of the protective layer material, and can be used as a protective layer in a touch display device. At the same time, compared with Comparative Example 1, the hardened films obtained in the present invention also have a higher transmittance and a certain haze value, and can be used as a haze layer in a touch display device. Therefore, the hardened film described in the present invention can take into account the performance of the protective layer and the haze layer, and integrate the protective layer and the haze layer in the original touch display device into one layer of material, simplifying the original preparation process and reducing production costs. In addition, the hardened film described in the present invention can also be used to prepare a touch display device with better display effect, meeting higher product requirements.

[0118] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A negative photosensitive resin composition, characterized in that: The composition includes the following components in parts by weight: 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.

2. A 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 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.

3. A 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 methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, hexyl methacrylate, 3-(methacryloyloxy)propyltrimethoxysilane, benzyl methacrylate, lauryl methacrylate, stearic methacrylate and dicyclopentyl methacrylate; The free radical initiator includes one or more of cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl perbenzoate, tert-butyl pervalerate, azobisisobutyronitrile and azobisisoheptylnitrile.

4. A negative photosensitive resin composition according to claim 3, characterized in that: The polymerization reaction temperature is 50-100° C. and the reaction time is 3-15 hours.

5. A negative photosensitive resin composition according to claim 4, characterized in that: The carbon-carbon double bond-containing composition is obtained by mixing a monofunctional monomer, a difunctional monomer and a multifunctional monomer; The monofunctional monomer includes one or more of methacrylic acid, hydroxyethyl methacrylate, dicyclopentenyl acrylate, ethoxyethoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, m-phenoxybenzyl methacrylate, tetrahydrofurfuryl acrylate, o-phenylphenoxyethyl acrylate, lauric methacrylate, stearic methacrylate, propoxylated nonylphenol acrylate, isodecyl acrylate, isooctyl acrylate, benzyl methacrylate and isobornyl methacrylate; The difunctional monomer includes one or more of tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, ethoxylated bisphenol A diacrylate and ethylene glycol dimethacrylate; The multifunctional monomer includes one or more of pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate and pentaerythritol hexaacrylate.

6. A negative photosensitive resin composition according to claim 5, characterized in that: The mass ratio of the monofunctional monomer, the difunctional monomer and the polyfunctional monomer is 40-70:10-40:5-15.

7. A negative photosensitive resin composition according to any one of claims 1 to 6, characterized in that: The polyhydroxy compounds include tris(2-hydroxyethyl)isocyanurate, 4',6,7-trihydroxyisoflavone, 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, 2,3,4-trihydroxybenzoic acid, One or more of 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, tetrahydroxypregnenolone, 2,2,5,5-tetrakis(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; The polycarboxyl compound includes one or more of 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-aminobenzene-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; The photoinitiator includes one or more of 1-hydroxycyclohexyl phenyl 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-morpholinyl-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, benzophenone, benzoylbenzoic acid, isopropylthioxanthone, benzyl dimethyl acetal, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trichloro-s-triazine, 2,2'-bis(2-chlorophenyl)-4,4' and 5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole; 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 3-methoxypropionic acid methyl ester.

8. A negative photosensitive resin composition according to claim 7, characterized in that: The negative photosensitive resin composition further comprises additives, and the additives comprise one or more of a leveling agent, a stabilizer, a cross-linking agent, a sensitizer, a curing agent, a dispersant, an adhesion aid and a defoaming agent.

9. The method for preparing a negative photosensitive resin composition according to any one of claims 1 to 8, characterized in that: The steps include: The components are mixed to obtain a negative photosensitive resin composition.

10. A hardened film, characterized in that: The negative photosensitive resin composition prepared by the method for preparing a negative photosensitive resin composition according to claim 9 is hardened.

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