Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes

Definitions

• the present invention relates to a thermosetting resin composition and a display device.
• An active matrix drive type liquid crystal display device provided with a thin film transistor (TFT: Thin Film Transistor), an active matrix drive type organic EL display device provided with an organic EL (Electro-Luminescence) element and a thin film transistor connected thereto.
• the display device is provided with a patterned electrode protective film, a planarizing film, an insulating film, and the like.
• a photosensitive resin composition is generally used as a material for forming these films, and among them, materials having excellent transparency with a small number of steps for obtaining a predetermined pattern shape are widely used.
• the electrode protective film, the planarizing film, and the insulating film described above are required to have various characteristics necessary for the display device. Specifically, it has excellent process resistance such as heat resistance, solvent resistance, reflow resistance and metal sputtering resistance, good adhesion to the substrate, and patterns under various process conditions according to the purpose of use. A wide process margin capable of forming a film, high sensitivity to light and high transparency, and little film unevenness after development. For this reason, conventionally, acrylic resins have been widely used.
• a glass substrate is used in the conventional display device.
• a resin substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide instead of a glass substrate.
• a resin substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide instead of a glass substrate has been studied. If a flexible display becomes possible by applying a resin substrate, the electrode protection film, the planarization film, and the insulating film are required to have high hardness from the viewpoint of increasing mechanical strength. Further, since the resin substrate has low heat resistance, the film formed on the resin substrate is required to be cured under a lower temperature process condition.
• Patent Document 1 discloses an acrylic resin having a carboxyl group and an epoxy group in the side chain. However, it is difficult to obtain sufficient hardness with an acrylic resin having such a crosslinked system with epoxy.
• Patent Document 2 proposes to increase the hardness by adding a polyfunctional acrylic monomer and silsesquioxane modified with an acryloyl group.
• this configuration is not practical because tacking occurs after pre-baking, and photocuring is required for curing.
• Patent Document 3 discloses a negative photosensitive resin composition comprising an acryloyl group-containing silsesquioxane, a carboxyl group-containing acrylate compound or oligomer, an acrylate compound, and a photopolymerization initiator.
• a film with high hardness cannot be obtained.
• an object of the present invention is to provide a thermosetting resin composition that, when cured, satisfies basic performance requirements for an electrode protective film, a planarizing film, and an insulating film, and becomes a film having high hardness at low temperatures. There is to do.
• Another object of the present invention is to provide a display device having excellent mechanical strength.
• thermosetting resin composition of the present invention is (A): an acrylic polymer having a side chain having an unsaturated bond at the terminal; (B): acid or thermal acid generator, (C): Silsesquioxane, (D): a compound having two or more vinyl groups directly bonded to the benzene ring, (E): Contains a solvent.
• the end of the side chain is preferably an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group.
• the content of the acid or thermal acid generator (B) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the acrylic polymer (A).
• the content of silsesquioxane (C) is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the acrylic polymer (A).
• the content of the compound having two or more vinyl groups directly bonded to the benzene ring is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the acrylic polymer (A).
• the display device of the present invention has a film obtained by curing the thermosetting resin composition of the present invention.
• thermosetting resin composition that satisfies the basic performance requirements for an electrode protective film, a planarizing film, and an insulating film by curing and becomes a film having high hardness at low temperature. Further, by providing a cured film obtained from this thermosetting resin composition, a high-quality display device having excellent mechanical strength is provided.
• thermosetting resin composition of the embodiment of the present invention is constituted by dissolving the following component (A), component (B), component (C) and component (D) in a solvent which is component (E).
• the component (A) is an acrylic polymer having a side chain having an unsaturated bond at the terminal. More specifically, it is an acrylic polymer having 3 to 16 carbon atoms and having a side chain having an unsaturated bond at the terminal (hereinafter referred to as a specific side chain) and being alkali-soluble.
• the acrylic polymer has a polystyrene-equivalent number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 50,000.
• the acrylic polymer refers to a polymer obtained by homopolymerizing or copolymerizing monomers having an unsaturated double bond such as acrylic ester, methacrylic ester and styrene.
• the acrylic polymer as the component (A) may be an acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.
• the acrylic polymer as the component (A) is more preferably one having a number average molecular weight in the range of 2,000 to 50,000. Furthermore, it is more preferable that the acrylic polymer of the component (A) is 200 to 1,300 g equivalent per 1 mol equivalent of the unsaturated double bond contained in the specific side chain.
• the specific side chain of the component (A) preferably has 3 to 16 carbon atoms and has an unsaturated bond at the terminal, and the specific side chain represented by the formula (1) is particularly preferable.
• the specific side chain represented by the formula (1) binds to the ester bond portion of the acrylic polymer as shown in the formula (1-1).
• R 1 is an aliphatic group having 1 to 10 carbon atoms, an aliphatic group having 3 to 14 carbon atoms including a cyclic structure, and an aromatic group having 6 to 14 carbon atoms.
• R 1 may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.
• R 2 represents a hydrogen atom or a methyl group.
• R 1 examples include the following formulas (A-1) to (A-11). Note that, in the formulas (A-1) to (A-11), the right terminal is the side that is bonded to the double bond.
• a specific side chain in which R 2 is a hydrogen atom is preferable, and a specific side chain in which a terminal is an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group is more preferable.
• the unsaturated double bond contained in the specific side chain represented by the formula (1) is contained in an amount of 1 mol equivalent to 200 to 1,300 g equivalent of the acrylic polymer of the component (A).
• the method for obtaining the acrylic polymer having the specific side chain as described above is not particularly limited.
• an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization.
• a specific compound a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to generate a specific side chain.
• a specific compound a compound having an unsaturated bond at the terminal
• the specific functional group means a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these functional groups.
• Specific compounds include, for example, glycidyl methacrylate, glycidyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, acrylic acid chloride, methacrylic acid, acrylic acid, m-tetramethylxylene diisocyanate, ⁇ , ⁇ - Examples include dimethyl m-isopropenyl benzyl isocyanate, allyl glycidyl ether, vinyl ethylene oxide, vinyl cyclohexene oxide, bromostyrene, and chlorostyrene.
• an example of a preferable structure is an acrylic polymer having a structural unit represented by the formula (2).
• R 1 is an aliphatic group having 1 to 10 carbon atoms or an aliphatic group having 3 to 14 carbon atoms including a cyclic structure as defined in the above formula (1). And an organic group selected from the group consisting of aromatic groups having 6 to 14 carbon atoms, or an organic group consisting of a combination of a plurality of organic groups selected from this group.
• R 1 may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.
• R 3 represents a hydrogen atom or a methyl group.
• the preferred combination of the specific functional group and the functional group of the specific compound that is involved in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, or a phenolic group.
• a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.
• the acrylic polymer having the specific functional group is a monomer having a functional group (specific functional group) for reacting with the specific compound, that is, carboxyl group, glycidyl group, hydroxy group.
• the monomer having the specific functional group used for the polymerization may be used alone, or a plurality of types may be used in combination as long as the combination does not react during the polymerization.
• Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
• Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide.
• Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Carboxymethyl-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-2-carboxylic
• Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
• Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide.
• Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, m-tetramethylxylene diisocyanate, and the like.
• a monomer having a non-reactive functional group that can be copolymerized with a monomer having a specific functional group can be used in combination.
• Examples of the monomer having a non-reactive functional group include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
• acrylic ester compounds methacrylic ester compounds
• maleimide compounds acrylonitrile
• maleic anhydride maleic anhydride
• vinyl compounds vinyl compounds.
• acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
• vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether.
• styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
• maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• the method for obtaining an acrylic polymer having a specific functional group is not particularly limited.
• the solvent used at this time is not particularly limited as long as it dissolves the monomer and polymerization initiator involved in the reaction. As a specific example, what is described in the solvent of the (E) component mentioned later is mentioned.
• the acrylic polymer having a specific functional group obtained as described above is usually in a solution state dissolved in a solvent.
• a specific compound is reacted with the obtained acrylic polymer having a specific functional group to obtain an acrylic polymer (hereinafter referred to as a specific copolymer) as component (A).
• the reaction with the specific compound is usually performed using a solution of an acrylic polymer having a specific functional group.
• a specific copolymer is prepared by adding glycidyl methacrylate to a solution of an acrylic polymer having a carboxyl group and reacting at a temperature of 80 to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride. Can be obtained.
• the solvent used at this time is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer.
• the specific copolymer obtained as described above is usually in a solution state dissolved in a solvent.
• dicarboxylic acid anhydrides examples include phthalic acid anhydride, trimellitic acid anhydride, naphthalene dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-methyl-1,2-cyclohexanedicarboxylic acid.
• the specific copolymer solution is re-precipitated by stirring under stirring such as diethyl ether or water, and after filtering and washing the generated precipitate, it is dried at normal temperature or reduced pressure at normal temperature or under heat, It can be set as the powder of a specific copolymer.
• the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer is obtained.
• movement what is necessary is just to redissolve the obtained powder in a solvent and to repeat said operation.
• the powder of the specific copolymer may be used as it is, or used after re-dissolving the powder of the specific copolymer in a solvent of the component (E) to be described later. May be.
• the acrylic polymer as the component (A) may be a mixture of a plurality of types of specific copolymers.
• thermosetting resin composition according to the embodiment of the present invention includes a component (B) described below.
• the component (B) is an acid or a thermal acid generator.
• the type of acid used in the thermosetting resin composition of the embodiment of the present invention is not particularly limited, but sulfonic acids are preferably used.
• Specific examples of the sulfonic acids include p-toluenesulfonic acid, n-propylsulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, and n-octanesulfonic acid.
• the thermal acid generator used in the thermosetting resin composition of the embodiment of the present invention is a compound that generates an acid by thermal decomposition during post-baking, specifically, an acid generated by thermal decomposition at 150 to 250 ° C. There is no particular limitation as long as it is a generated compound.
• Examples of such compounds include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris ( Methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid Isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-tol
• thermal acid generators such as sulfonic acids are preferable because they do not affect the transparency and are easy to improve thermosetting.
• the content of the component (B) in the thermosetting resin composition of the embodiment of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 100 parts by mass of the component (A). Thru
• the amount is less than 0.1 parts by mass, the thermosetting speed is slow, and the pencil hardness of the cured film formed using the thermosetting resin composition may be lowered.
• thermosetting resin composition includes a component (C) described below.
• Component (C) is silsesquioxane, which is polysiloxane represented by [(RSiO 3/2 ) n ].
• the structure of the component (C) may be any of a random structure, a ladder type structure, a complete cage type structure or an incomplete cage type structure, and is not particularly limited.
• (C) component can be made into the silsesquioxane which consists of single or 2 types or more of combinations.
• Silsesquioxane is usually produced by a sol-gel method in which trialkoxysilane is hydrolyzed. By changing the type of trialkoxysilane used as a raw material, silsesquioxanes having different properties can be obtained.
• trialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2- Aminoethyl) trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,
• n- hexyl trimethoxy silane and n- hexyl triethoxy silane are used alone or in combination of two or more.
• 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3- Silsesquioxane formed by using acryloxypropyltrimethoxysilane is preferable from the point of reacting with the component (A) during thermosetting.
• the content of the component (C) in the thermosetting resin composition of the embodiment of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 15 to 60 parts by mass.
• the amount is less than 5 parts by mass, the hardness of the cured film formed using the thermosetting resin composition may be low.
• the coating film after pre-baking may be tacky. There is.
• thermosetting resin composition of the embodiment of the present invention contains (D) component described below.
• Component (D) is a compound having two or more vinyl groups bonded directly to a benzene ring.
• the thermosetting property with the component (A) can be improved and the hardness can be improved.
• Specific examples of the compound having two or more vinyl groups directly bonded to the benzene ring include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 4,4′-divinylbiphenyl, Tris- (4-vinylphenyl). ) Methane and 4,4′-oxybis (vinylbenzene).
• the compound having two or more vinyl groups directly bonded to the benzene ring of component (D) can be used alone or in combination of two or more.
• the content of the component (D) in the thermosetting resin composition of the embodiment of the present invention is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 5 to 20 parts by mass.
• the amount is less than 1 part by mass, the pencil hardness of the cured film formed using the thermosetting resin composition may decrease. Moreover, when it exceeds 40 mass parts, a tack
• thermosetting resin composition includes a component (E) described below.
• the (E) component solvent used in this thermosetting resin composition dissolves the (A) component, the (B) component, the (C) component, and the (D) component, and is added as desired (described later).
• F) component, (G) component and other components are dissolved.
• the type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability.
• thermosetting resin composition of the embodiment of the present invention examples of a preferable solvent for the component (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol.
• propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate and butyl lactate, etc. have good coating properties and are safe From the viewpoint of high properties. These are generally used as solvents for photoresist materials.
• thermosetting resin composition of the embodiment of the present invention is constituted by dissolving the component (A), the component (B), the component (C) and the component (D) in the solvent of the component (E).
• the (F) component and (G) component which are demonstrated below, respectively.
• (F) component is an adhesion promoter.
• adhesion promoter By using the adhesion promoter, it is possible to improve the adhesion between the cured film formed using the thermosetting resin composition and the substrate after development.
• adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylvinylethoxysilane, and diphenyldimethoxysilane.
• chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylvinylethoxysilane, and diphenyldimethoxysilane.
• Alkoxysilanes such as phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine and trimethylsilylimidazole, vinyltrichlorosilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (N-pipe Silanes such as dinyl) propyltriethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole and mercaptopyrimidine Mention may be made of heterocyclic compounds
• adhesion promoter can be used as the adhesion promoter.
• a silane coupling agent and marketed may be obtained and used.
• Specific examples of such products include Z-6011, 6020, 6023, 6026, 6050, 6094, 6610, 6883, 6675, 6676, 6040, 6041, 6042, 6043 manufactured by Toray Dow Corning Silicone Co., Ltd. 6044, 6920, 6940, 6075, 6172, 6300, 6519, 6550, 6825, 6030, 6033, 6530, 6062, 6911 or 6860, KBM-1003, KBE-1003, KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.
• KBM-403, KBE-402, KBE-403, KBM-1403 KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM -903, KBE- 103, KBM-573, KBM-575, KBM-6123 or KBE-585, A-151, A-171, A-172, A-2171, Y-9936, A-174, A-186, manufactured by MOMENTIVE A-187, A-1871, A-189, A-1891, A-1100, A-1110, A-1120, A-2120, Y-9669 or A-1160.
• the addition amount of the component (F) in the thermosetting resin composition of the embodiment of the present invention is usually 20 parts by mass or less, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 0.5 to 10 parts by mass. If it is used in excess of 20 parts by mass, the heat resistance of the coating film may be reduced, and if it is less than 0.01 part by mass, sufficient effects of the adhesion promoter may not be obtained.
• thermosetting resin composition of the embodiment of the present invention is a surfactant.
• surfactant By using the surfactant, the applicability of the thermosetting resin composition can be improved.
• a component can be used individually or in combination of 2 or more types.
• the surfactant which is the component (G) in the embodiment of the present invention is not particularly limited as long as it does not impair the effects of the present invention.
• a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned.
• This type of surfactant is easily available from, for example, Sumitomo 3M Co., Ltd., DIC Co., Ltd. (former Dainippon Ink and Chemicals) or Asahi Glass Co., Ltd. Specific examples thereof include F-top [registered trademark] EF301, EF303, and EF352 (above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
• the content is usually 1.0 part by mass in 100 parts by mass of the thermosetting resin composition. Or less, preferably 0.5 parts by mass or less.
• the amount of the surfactant (G) used is set to an amount exceeding 1.0 part by mass, the coating property improvement effect expected in response to the increase in the content cannot be obtained. In other words, an inefficient use method will be performed.
• thermosetting resin composition of the embodiment of the present invention can contain the component (F) and the component (G), but further, unless the effects of the present invention are impaired. If necessary, other components can also be contained.
• Other components include additives such as rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.
• thermosetting resin composition An acrylic polymer having a side chain having an unsaturated bond at the terminal as the component (A); (B) an acid or thermal acid generator as a component; (C) Silsesquioxane as component, (D) a compound having two or more vinyl groups directly bonded to the benzene ring as a component; (E) It is comprised by melt
• This thermosetting resin composition is further, if desired, (F) Adhesion promoter as component, As the component (G), one or more of the above-described additives can be further contained as a surfactant and the other components.
• thermosetting resin composition of embodiment of this invention is as follows. [1] Based on 100 parts by mass of component (A), 0.1 to 30 parts by mass of component (B), 5 to 100 parts by mass of component (C), 1 to 50 parts by mass of component (D) These are thermosetting resin compositions dissolved in the solvent of component (E). [2] The thermosetting resin composition according to [1] above, further comprising 0.5 to 10 parts by mass of component (F) based on 100 parts by mass of component (A). [3] The thermosetting resin composition further comprising (G) component in an amount of 0.5 parts by mass or less with respect to 100 parts by mass of the thermosetting resin composition in the composition of [1] or [2]. object.
• the ratio of the solid content in the thermosetting resin composition of the embodiment of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, it is 1 to 80% by mass, and for example 5 to 60% by mass, or 10 to 50% by mass.
• solid content means what remove
• the method for preparing the thermosetting resin composition of the embodiment of the present invention is not particularly limited.
• the component (A) (acrylic polymer) is dissolved in the solvent of the component (E), the component (B) (acid or thermal acid generator), the component (C) (silsesquioxane) , (D) component (compound having two or more vinyl groups directly bonded to the benzene ring) is mixed at a predetermined ratio to obtain a uniform solution.
• a preparation method in which (F) component (adhesion promoter), (G) component (surfactant) and other components are further added and mixed as necessary. .
• the solution of the specific copolymer obtained by the polymerization reaction in the solvent of the component (E) can be used as it is.
• the solvent of the component (E) used in the process of forming the specific copolymer and the solvent of the component (E) used for concentration adjustment when preparing the thermosetting resin composition may be the same. It may be different or different.
• thermosetting resin composition in a solution state after filtration using a filter having a pore diameter of about 0.2 ⁇ m.
• a semiconductor substrate such as a silicon substrate or a silicon nitride substrate is prepared.
• a glass substrate or a quartz substrate may be used instead of the semiconductor substrate.
• a silicon dioxide film, an ITO (Indium Tin Oxide) film, or a metal film such as aluminum, molybdenum, or chromium may be formed on the substrate.
• thermosetting resin composition of the embodiment of the present invention is applied by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, or inkjet coating. Subsequently, a coating film can be formed by predrying with a hot plate or oven. Then, this coating film is heat-treated.
• a heating temperature and a heating time appropriately selected from the range of a temperature of 70 to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
• the film obtained above is post-baked for thermosetting.
• a cured film having excellent heat resistance, transparency, planarization, low water absorption, chemical resistance, and the like can be obtained by heating using a hot plate or an oven.
• post-baking is performed at a heating temperature selected from a temperature range of 140 to 250 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. The method is taken.
• the cured film obtained by post-baking is characterized by high hardness, excellent heat resistance and solvent resistance, and high transparency. Therefore, it can be suitably used for various films in liquid crystal displays and organic EL displays, for example, interlayer insulating films, protective films, insulating films and the like. Further, it is also suitably used in applications such as an array flattening film for TFT type liquid crystal elements.
• Examples 1 to 5 and Comparative Examples 1 to 4 In accordance with the composition shown in the following Table 1, (B) component and (C) component, and (D) component, (E) component and (G) component are mixed in a predetermined ratio to component (A) solution.
• the thermosetting resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.
• thermosetting resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 For the obtained thermosetting resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4, the presence or absence of tack in the coating film after pre-baking, pencil hardness of the cured film, transmittance, and solvent resistance were measured. And evaluated them.
• thermosetting resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.0 ⁇ m.
• the surface of this coating film was touched with tweezers.
• thermosetting resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.0 ⁇ m.
• This coating film was post-baked by heating at 180 ° C. for 30 minutes and at 230 ° C. for 30 minutes to form a cured film having a thickness of 1.8 ⁇ m.
• the pencil hardness used when the surface of each coating film was not damaged at a load of 500 g was defined as the pencil hardness.
• thermosetting resin composition was applied on a quartz substrate using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.0 ⁇ m.
• This coating film was irradiated with ultraviolet rays having a light intensity of 365 mW / nm 2 at 365 nm for 90 seconds by an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc.
• This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.
• the cured film was measured for transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).
• thermosetting resin composition was applied onto a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 2.0 ⁇ m.
• This coating film was post-baked by heating at 180 ° C. for 30 minutes to form a cured film having a thickness of 1.8 ⁇ m.
• This coating film was immersed in NMP for 1 minute at room temperature.
• thermosetting resin compositions of Examples 1 to 5 showed tack after pre-baking. Further, the pencil hardness after curing at 180 ° C. was as high as 3H or higher, and there was no problem with the transmittance and solvent resistance.
• Comparative Example 1 the pencil hardness was as low as B. About the comparative example 2, tack entered after prebaking and it did not result in subsequent evaluation. In Comparative Example 3, the pencil hardness was as low as B, and solvent resistance was not obtained. For Comparative Example 4, the transmittance and solvent resistance were good, but the pencil hardness after curing at 180 ° C. was as low as 2H.
• thermosetting resin composition according to the present invention is suitable as a material for forming a protective film, a planarizing film, an insulating film, etc. in a display device including a thin film transistor (TFT) type liquid crystal display element or an organic EL element. It is suitable for a display device provided with a touch panel or a display device using a resin substrate. For example, it is suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array flattening film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, and the like.

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