TWI413864B - Silsesquioxane-containing compound and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silsesquioxane-containing compound which can impart various desired functions such as photopolymerization, alkali solubility and weatherability and is suitable for a radiation-sensitive resin having characteristics of silicon resins such as transparency and heat resistance. <P>SOLUTION: The silsesquioxane-containing compound is obtained by the cocondensation of a copolymer of (A) a (meth)acrylic ester having a trialkoxysilyl group in the molecule and at least one of a (meth)acrylic ester having a functional group capable of imparting alkali solubility as a substituent and a (meth)acrylic ester having a functional group capable of imparting heat resistance as a substituent with a trialkoxysilane compound (C') having a carbon-carbon double bond in the molecule. The radiation-sensitive resin uses the compound. A method for producing the compound comprises performing the radical copolymerization of vinyl monomers and successively performing the cocondensation with a trialkoxysilane. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

Compound containing sesquiterpene oxide and preparation method thereof

The present invention relates to a sesquiterpene oxide compound having an acrylic copolymer chain, and more particularly to a sesquiterpene oxide-containing compound capable of imparting various desired functions such as photopolymerizability, alkali solubility, heat resistance, weather resistance, and the like. And it is suitable for a thermal radiation-linear resin because it has the characteristics of a fluorene-based resin such as transparency and heat resistance; and the method for producing the compound is carried out by performing a radical copolymerization of a vinyl monomer followed by a trialkoxy decane. Co-condensation.

In recent years, in the field of display elements such as liquid crystals and LEDs, it has high transparency (that is, high visible light transmittance. The same applies hereinafter) and has good heat resistance, radiation sensitivity, development resolution, and chemical resistance. The demand for thermal radiation linear resins is rising. In particular, it is difficult to satisfy the requirements of a conventional photosensitive resin such as a phenol resin, a phenol resin for lacquer, an acrylic copolymer resin, or an alicyclic alkyl resin because of high transparency. That is to say, the conventional resin cannot sufficiently satisfy the high transparency (including both the transparency at the time of film formation of the coating film and the heat-resistant transparency of transparency after heating). In order to solve this problem, there have been several examples in which a lanthanoid resin is used in order to have good transparency and heat resistance.

A thermoradiographic resin containing a sesquiterpene oxide structure has been disclosed as a photoresist resin containing a copolymer of a ladder sesquiterpene structure (for example, see Patent Document 1). The copolymer is obtained by co-condensing a trialkyloxy decane having a side chain, and then synthesizing a sesquiterpene oxide having a ladder-like structure of a vinyl side chain, and then decomposing the organic acid by the acid. The acrylic monomer of the side chain of the base is obtained by copolymerization with a sesquiterpene oxide containing the above vinyl side chain, and the polymer is used as a positive type resist. However, since the copolymer is subjected to radical copolymerization by synthesizing a sesquioxane by co-condensation, the acrylic monomer is completely consumed, so that the ethylenic double bond in the compound is completely consumed, so that photopolymerization cannot be exerted, and there is no negative The function of the type of photoresist. Further, the ladder sesquiterpene oxide structure is advantageous in that it is a positive photoresist, although it has a high niobium content and good thermal stability or oxygen plasma resistance, but it is still insufficient in terms of high transparency and heat resistance.

Further, an alkali-soluble photosensitive resin using a (meth)acryloxy functional ladder-like sesquiterpene alkane is known (for example, see Patent Document 2). The sesquiterpene oxide contains not only a side chain such as an alkyl group, an aryl group or a cyclohexyl group, but also a (meth) propylene fluorenyloxy group, which is composed of a (meth) acryloxy group-containing trialkoxy decane and a The side chain-based trialkoxy decane is co-condensed. However, the sesquiterpene alkane itself does not have alkali solubility. Moreover, there is no disclosure at all about the compound containing a sesquiterpene oxide containing a radical copolymer chain.

Further, a photoresist composition using a sesquioxane having a carboxyl group in a side chain is known (for example, see Patent Document 3). However, the sesquiterpene oxide does not have photopolymerizability. Moreover, there is no disclosure at all about the compound containing a sesquiterpene oxide containing a radical copolymer chain. As described above, the sesquioxalic acid compound suitable for the heat radiation linear resin is still unknown until it has high transparency and satisfies the basic physical properties of the photoresist.

[Patent Document 1] WO99/09457, pages 37 to 39, and the like.

[Patent Document 2] Japanese Laid-Open Patent Publication No. Hei 10-161315, page (4), and the like.

[Patent Document 3] Japanese Laid-Open Patent Publication No. Hei 11-60734, the scope of which is incorporated herein by reference.

In view of the above circumstances, an object of the present invention is to provide a compound containing sesquiterpene oxide which imparts various functions required for photopolymerization, alkali solubility, heat resistance, weather resistance, and the like, and is suitable for both transparency. a heat radiation linear resin characterized by a heat-resistant lanthanide resin; and a method for producing a compound containing sesquiterpene oxide, which is followed by radical copolymerization of a vinyl monomer followed by a trial of a trialkoxy decane Condensation to give the compound a high degree of design freedom.

The present inventors have diligently studied in order to solve the above problems, and as a result, it has been found that high-design freedom of a sesquiterpene-containing oxane compound can be ensured by radical copolymerization of a vinyl monomer followed by co-condensation of a trialkoxy decane. Based on this finding, a manufacturing method capable of freely imparting various functions of sesquiterpene oxide was found, and the present invention was completed. That is, the present invention is a sesquiterpene-containing compound which is a (meth) acrylate (A) having a trialkoxycarbenyl group in the molecule and a (meth)acrylic acid which may have a substituent. The ester (B) is copolymerized into a copolymer (I), and the copolymer (I) is obtained by co-condensing a trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule.

The present invention is also a heat radiation linear resin composition containing the above alkali-soluble compound.

The present invention is also an electronic component or a substrate for an optical component having a hardened layer of the above composition.

The present invention is also a process for producing a compound containing a sesquiterpene oxide, which comprises (1) a (meth) acrylate (A) having a trialkoxycarbenyl group in a molecule and a (meth) group which may have a substituent a process for copolymerizing acrylate (B), and (2) a process for co-condensing the obtained copolymer with a trialkoxy decane compound (C) which may contain an ethylene carbon-carbon double bond in the molecule.

The present invention has the following effects due to the above configuration.

(1) The sesquiterpene-containing compound of the present invention can impart various desired functions such as photopolymerization, alkali solubility, heat resistance, and weather resistance.

(2) The sesquioxane-containing compound of the present invention is excellent in transparency and heat resistance.

(3) The sesquiterpene-containing compound of the present invention can provide a heat radiation linear resin excellent in transparency and heat resistance.

(4) The heat radiation linear resin of the present invention has characteristics such as good heat resistance, high transparency, radiation sensitivity, development resolution, and chemical resistance.

Hereinafter, the present invention will be described in detail.

In the present invention, the (meth) acrylate (A) having a trialkoxycarbenyl group in the molecule is, for example, 3-methylpropenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropyl group. Triethoxy decane, 3-propenyl methoxypropyl trimethoxy decane, 3-propenyl methoxypropyl triethoxy decane, and the like.

The (meth) acrylate (B) which may have a substituent contains a (meth) acrylate having no substituent and a (meth) acrylate having a substituent, and the above substituent is not particularly limited and may have a correspondence A substituent which is intended to impart functionality to a compound containing sesquiterpene. For example, a functional group capable of imparting alkali solubility to a compound containing sesquiterpene oxide and a functional group capable of imparting at least one of heat resistance and weather resistance to a compound containing sesquiterpene oxide can be selected.

The (meth) acrylate having such a substituent is, for example, a (meth) acrylate (b-1) having a functional group capable of imparting alkali solubility to a compound containing a sesquiterpene oxide, for example, , 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxyethyl hexahydrophthalate, β-carboxyethyl acrylate, ω-carboxyl poly(acrylic acid) Caprolactone, ethylene oxide-modified succinic acid acrylate, and the like. These may be used alone or in combination of two or more.

(meth) acrylate (b-2) which is a substituent capable of imparting at least one of heat resistance and weather resistance to a compound containing sesquiterpene oxide, for example, bicyclo(meth)acrylate Amyl ester, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 9-methylpropenylmethoxymethylhydrazine, tetrahydrofurfuryl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

The other (meth) acrylate (B) which may have a substituent may, for example, be a (meth) acrylate (b-3) which has a functional group capable of imparting adhesion to a compound containing a sesquiterpene oxide as a substituent. ), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxy 2-ethylhexyloxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, caprolactone, (a) Base) methoxy diethylene glycol acrylate, methoxy triethylene glycol (meth) acrylate, decyl phenoxy propylene glycol (meth) acrylate, hydroxyethyl vinyl ether, etc.; a (meth) acrylate (b-4) which is a substituent which imparts a property of at least one of a miscibility and a hydrophobicity to a compound containing a sesquioxanes, for example, cyclohexyl (meth)acrylate , benzyl (meth) acrylate, butoxyethyl (meth) acrylate, cetyl methacrylate, ethyl (meth) acrylate, glyceryl (meth) acrylate, glycidyl (meth) acrylate Ester, (meth)acrylic acid, hexafluoropropyl ester, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(methyl)propene oxime base Oxetane, isobutyl (meth)acrylate, isodecyl (meth)acrylate, lauryloxypolyethylene glycol (meth)acrylate, lauryl (meth)acrylate, (methyl) Methoxypolyethylene acrylate, methyl (meth) acrylate, pentamethylpiperidine (meth) acrylate, phenoxyethyl (meth) acrylate, stearyl (meth) acrylate, (methyl) Isostearyl acrylate, tert-butyl (meth)acrylate, tetramethylpiperidine (meth)acrylate, moringichyl (meth)acrylate, triethylene glycol divinyl ether, octadecyl a vinyl ether or the like; a (meth) acrylate (b-5) which is a substituent capable of imparting flame retardancy to a compound containing a sesquiterpene oxide, for example, tribromophenyl (meth) acrylate , EO modified tribromophenyl ester, and the like. These may be used alone or in combination of two or more kinds, and the above esters (b-3) to (b-5) may be used in combination. The above esters (b-1) to (b-5) may also be used in combination.

The copolymerization of the (meth) acrylate (A) and the (meth) acrylate (B) can be carried out according to a usual method, and a known method such as solution polymerization, suspension polymerization or emulsion polymerization can be used, from the viewpoint of ease of handling, Good solution polymerization. When the copolymer of the present invention is produced by a solution polymerization method, first, a polymerization initiator is dissolved in a monomer mixture of the above (meth) acrylate (A) and (meth) acrylate (B), and dissolved as needed. Chain transfer agent. Then, the obtained homogeneous mixture is maintained at a predetermined polymerization temperature for a certain period of time to complete the polymerization, and a copolymer can be obtained.

The polymerization initiator which can be used at this time preferably has a 10-hour half-life temperature in the range of 60 to 120 °C. Such polymerization initiators are, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis ( 2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-cyanohexyl-2-methylpropionamide), Azo such as 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]; 1,1,3,3-tetramethylbutyl peroxy-2-oxide Ethyl ester, 1-cyclohexyl-1-methylethylperoxide 2-ethyl hexanoate, dihexylperoxyperoxide 2-ethyl hexanoate, hexyl pentyl-peroxide 2-ethyl hexanoate Acid tert-butyl-peroxide 2-ethyl ester, tert-butyl-peroxide isobutyrate, tert-butylperoxide maleic acid, hexanoic acid third pentyl peroxide 3,5,5-three Methyl ester, butyl hexanoate peroxy 3,5,5-trimethyl ester, tert-butylperoxylaurate, third hexyl peroxybenzoate, tert-butyl peroxyacetate a peroxy ester such as t-butyl peroxym-toluoyl benzoate or t-butyl peroxybenzoate; a third hexylperoxy isopropyl monocarbonate and a third butyl group Peroxymonocarbonate such as isopropyl monocarbonate or tert-butylperoxy 2-ethylhexyl monocarbonate; bis-3,5,5-trimethylhexyl peroxide, octyl sulfhydryl Oxide, lauryl peroxide, stearyl peroxide, succinic peroxide, m-toluene peroxide, benzhydryl peroxide, p-chlorobenzoyl peroxide, etc. Dimethyl peroxides; dialkyl peroxides such as dicumyl peroxide and t-butyl cumyl peroxide. These may be used alone or in combination of two or more.

The amount of the (meth) acrylate (A) component in the copolymer (I) is preferably from 5 to 95% by mass. When the compounding amount of the (meth) acrylate (A) component falls within the above range, it is advantageous in terms of heat resistance, transparency, and mechanical strength of the compound containing sesquiterpene oxide. More preferably 5 to 50% by mass.

The amount of the (meth) acrylate (B) component in the copolymer (I) is preferably from 5 to 95% by mass, more preferably from 50 to 70% by mass, based on the carboxylic acid-containing monomer, and the other monomer is preferably 0. ~50% by mass.

The weight average molecular weight of the copolymer (I) is preferably from 1,000 to 50,000. If the weight average molecular weight exceeds 50,000, gelation may occur when co-condensed with the trialkoxydecane compound (C), whereas if it is less than 1000, the development rate of the compound containing sesquiterpene may be too fast. This makes it difficult to control alkali solubility or to obtain sufficient heat resistance. More preferably, it is 4,000 to 40000, and more preferably 7,000 to 30,000.

In the present invention, the trialkoxy decane compound (C) which may contain an ethylenic carbon-carbon double bond in the molecule includes a trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule and a molecule A trialkoxy decane compound which does not contain an ethylene carbon-carbon double bond. The trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule is, for example, 3-methylpropenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxylate. (Meth) propylene decyloxyalkoxy decane, vinyl trimethoxy decane, p-styryl trimethoxy decane, etc., such as decane or 3-propenyl methoxypropyltrimethoxy decane. These may be used alone or in combination of two or more.

A trialkoxy decane compound having no ethylenic carbon-carbon double bond in the molecule, for example, phenyltrimethylnonane, methyltrimethoxydecane, 2-(3,4 epoxy)cyclohexylethyltrimethoxy Baseline, 3-glycidoxypropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropane Triethoxy decane, 3-triethoxycarbamido-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3- An alkyl group or an aryl functional group such as ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropyltrimethylnonane, 3-isocyanatepropyltriethoxydecane At least one or more of the constituent monomers may be used.

The co-condensation of the copolymer (I) with the trialkoxy decane compound (C) can be carried out by a usual method, by hydrolyzing the alkoxymethyl hydrazine group in the presence of an acidic catalyst, and by dehydration condensation reaction of the decyl alcohol group. A siloxane chain is formed. The amount of water to be blended at this time is preferably a molar number of alkoxycarbenyl group, and is 1.0 to 3.0. When the molar ratio of the molar amount falls within the range, the obtained sesquioxanes-containing compound is a mixture of a ladder-like or random structure mainly containing a cage structure.

As the above acidic catalyst, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or the like can be used. A fluorine-based compound such as tetrabutylammonium fluoride, potassium fluoride or sodium fluoride can also be used. The compounding amount is preferably from 0.01 to 0.1% by weight.

The reaction temperature of the co-condensation reaction is 40 to 80 ° C, and the reaction time is preferably 3 to 12 hours.

The method for producing a sesquiterpene oxide-containing compound of the present invention is as described above, wherein the copolymerization of the acrylic monomer is carried out, and then the alkoxymethyl hydrazine is hydrolyzed and dehydrated to carry out co-condensation, so that (i) is easy. The introduction of a carbon-carbon double bond to the target compound and (ii) the use of a comonomer having various substituents can easily impart desired properties to the target compound, and therefore, the method has a great degree of freedom in designing the target compound. For example, the (meth) acrylate (B) uses a substituent which is a (meth) acrylate (b-1) capable of imparting an alkali-soluble functional group to a compound containing a sesquiterpene oxide, and the substituent is a double The (meth) acrylate (b-2) which imparts a functional group having at least one of heat resistance and weather resistance to at least one of heat resistance and weather resistance, and at least one of alkali solubility, heat resistance and weather resistance can be imparted to the target compound. Further, by co-condensing a trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule, photopolymerizability can be imparted to the target compound. The alkali-soluble sesquiterpene-containing compound is suitable as a negative-type thermal radiation linear resin composition. Further, when the trialkoxydecane compound (C) is a monomer composed of the above alkyl group or an aryl functional group, it is suitably used as a positive thermal radiation linear resin composition.

The photopolymerization initiator (E), the crosslinking agent (F), and the surfactant (G) may be blended in the above thermally radiation-linear resin composition. The photopolymerization initiator (E) is, for example, a thioxanthone such as thioxanthone or 2,4-diethylthioxanthone; 4,4'-dimethylaminobenzophenone, 4 , benzophenones such as 4'-diethylaminobenzophenone; 2,2-diethoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 2 -methyl[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Acetophenones such as alkyl-1-ketones; halides such as 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2,4, a mercaptophosphine oxide such as 6-trimethylbenzimidyldiphenylphosphine oxide; and 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone Oxide, etc.

The amount of the photopolymerization initiator (E) is preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight based on the total mass of the thermally radiation-linear resin composition.

The above crosslinking agent (F) is, for example, 1,6-hexanediol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(a) Poly(butylene glycol) acrylate, 1,3-butylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triisopropyl glycol di(meth)acrylate, Poly(ethylene glycol) (meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tris(meth)acrylate, monohydroxytris(methyl) Pentaerythritol acrylate, trimethylolpropane triethoxytri(meth) acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth) acrylate, monohydroxy five ( Dipentaerythritol methyl methacrylate, dipentaerythritol hexa(meth) acrylate, ethylene oxide trimeric isocyanate (hereinafter referred to as EO) denatured tris(meth) acrylate, trimethylolpropane EO denatured three (a) ) Acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, polyhydric esters of various aminomethane (meth) acrylate esters of polyols, and various (meth) acrylate. Commercially available products of East Asia Synthetic Co., Ltd. and Nippon Kayaku Co., Ltd. can be used as the polyfunctional (meth) acrylate monomer or oligomer.

The amount of the crosslinking agent (F) is preferably 20% by weight or less, and more preferably 10% by weight or less based on the entire amount of the thermally radiation-linear resin composition.

The above surfactant (G) is, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyethylene oxide oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene decyl benzene Polyoxyethylene aryl ethers such as ether; polyoxyethylene dialkyl ester nonionic surfactants such as polyoxyethylene dilaurate or polyoxyethylene distearate; Yevtop EF301, Yevto 303, Yevtop 352 (New Akita Chemicals Co., Ltd.); US$F171, Mecca F172, Mecca F173 (Daily Ink Chemical Industry Co., Ltd.); Flora FC- 430, Flora FC-431 (Sumitomo 3M Co., Ltd.); Asadian Plus AG710, Safran S-382, Saflon SC-101, Saflon SC-102, Saflon SC-103, Saflon SC-104, Saflon SC-105, Saflon SC-106 (Asahi Glass Co., Ltd.) and other names of commercially available fluorine-based surfactants; organic siloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.); (meth)acrylic copolymer Polyfro No. 57, No. 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

The above surfactant (G) is used to improve the coatability of the heat radiation linear resin composition of the present invention containing a solvent.

The amount of the surfactant (G) to be added is preferably 2% by weight or less, and more preferably 1% by weight or less based on the total amount of the thermally radiation-linear resin composition.

In the above thermally radiation-linear resin composition, other components may be blended insofar as the object of the present invention is not impaired. Examples of the other components include a solvent, an antistatic agent, a storage stabilizer, an antifoaming agent, a pigment, a dye, and the like.

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other glycol ethers; methyl 2-ethoxyethanol acetate, B Alkenylene dialkyl such as 2-ethoxyethanol acetate, butyl 2-ethoxyethanol acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate An alkyl ether acetate; an aromatic hydrocarbon such as toluene or xylene; a ketone such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, acetic acid Ethyl ester, butyl acetate, methyl lactate, lactic acid Ester such as ethyl ester. These solvents may be used alone or in combination of two or more.

The above-mentioned heat radiation linear resin composition is applied onto the surface of the substrate, and the solvent is removed by heating to form a coating film. When a photosensitive resin composition is applied to the surface of the substrate, a well-known method such as a spin coating method, a roll coating method, or a immersion method can be used. Next, the coating film is heated (prebaked) in a hot plate or an oven.

The substrate is not particularly limited. For example, there are various substrates such as electronic components and optical components. Specifically, for example, there are transparent insulating films formed between THT and transparent electrodes, and display elements such as liquid crystal display elements and PDPs. A substrate or the like in an optical component or an optical component.

Thereafter, the pre-baked coating film is irradiated with ultraviolet rays or the like through a mask of a predetermined pattern, and then developed with a developing solution to remove unnecessary portions, thereby forming a film having a predetermined shape. Examples of the developing solution include inorganic bases such as sodium carbonate, sodium hydroxide, and potassium hydroxide; and aqueous solutions such as an organic base such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. Further, methanol, ethanol, a surfactant, or the like may be appropriately added to the aqueous alkali solution. The developing method may be any one of a soaking method, a spraying method, and a spraying method, and the developing time is usually 30 to 240 seconds. After development, it is washed with a water stream and dried to form a pattern.

Thereafter, the pattern is further heated by a heating plate and an oven (post-baking) to further crosslink the unreacted components, and at the same time, the solvent is completely removed, and a predetermined film pattern can be obtained. The post-baking conditions vary depending on the type of the ingredients and the mixing ratio, and are usually 180 to 220 ° C, for example, 5 to 30 minutes for the heating plate, and 30 to 90 minutes for the oven.

In summary, an electronic component or a substrate for an optical component having the hardened layer of the above-described thermally radiation-linear resin composition can be obtained.

The present invention will be further described in detail by the following examples, but the invention is not limited thereto.

Example 1

Synthesis of alkali-soluble sesquiterpoxy-containing compound D-1 6.1 g of propylene hexahydrophthalate hexahydrophthalate was added to a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. - 4.7 g of methacrylic acid methoxypropyl trimethoxy decane, 20.0 g of benzyl methacrylate, 1.3 g of 2,2'-azobisisobutyronitrile, 1.3 g of β-mercaptopropionic acid, and 137 g of toluene. After nitrogen cleaning for 30 minutes, the flask was placed in an oil bath, and polymerization was carried out at an internal temperature of 80 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain a copolymer solution. Next, 100 g of the obtained polymer solution, 12.9 g of 3-acryloxypropyltrimethoxydecane, and 7.1 g of methyltrimethoxydecane were placed in a flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. 30 g of isopropyl alcohol was added dropwise to an aqueous solution of 5 g of distilled water, 0.3 g of 36% hydrochloric acid and 5 g of propanol at an internal temperature of 70 ° C for 30 minutes, and the reaction was carried out for 3 hours. After cooling to room temperature, 3 g of an adsorbent Qiwalai 500 (trade name, the same applies hereinafter) was added, and the mixture was stirred for 15 minutes to neutralize. After filtration and concentration, the compound D-146.4 g of an alkali-soluble sesquiterpoxide was obtained. The weight average molecular weight (hereinafter referred to as Mw) of the obtained resin was 17,200.

Example 2

Synthesis of alkali-soluble sesquiterpene-containing compound D-2 6.1 g of propylene hexahydrophthalate hexahydrophthalate was added to a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. - 4.7 g of methacrylic acid methoxypropyl trimethoxy decane, 20.0 g of isobornyl acrylate, 1.3 g of 2,2'-azobisisobutyronitrile, 1.3 g of β-mercaptopropionic acid, and 137 g of toluene, for 30 minutes After nitrogen purge, the flask was placed in an oil bath, and polymerization was carried out at an internal temperature of 80 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain a copolymer solution. Next, 100 g of the obtained polymer solution, 6.5 g of 3-acryloxypropyltrimethoxydecane, and 13.5 g of methyltrimethoxydecane were placed in a flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. 30 g of isopropyl alcohol was added dropwise to an aqueous solution of 5 g of distilled water, 0.3 g of 36% hydrochloric acid and 5 g of isopropyl alcohol at an internal temperature of 70 ° C for 30 minutes, and the reaction was carried out for 3 hours. After cooling to room temperature, 500 3 g of adsorbent Qiwa was added and stirred for 15 minutes to neutralize. After filtration and concentration, 38.0 g of an alkali-soluble sesquiterpoxide-containing compound D-2 was obtained. The Mw of the obtained resin was 15,500.

Example 3

Synthesis of alkali-soluble sesquiterpoxy-containing compound D-3 6.1 g of propylene hexahydrophthalate hexahydrophthalate was added to a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. - methacrylic acid methoxypropyl trimethoxy decane 4.5 g, cyclohexyl methacrylate 20.0 g, β-mercaptopropionic acid 1.3 g, 2,2'-azobisisobutyronitrile 1.3 g, toluene 137 g, After nitrogen cleaning for 30 minutes, the flask was placed in an oil bath, and polymerization was carried out at an internal temperature of 80 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain a copolymer solution. Next, 100 g of the obtained polymer solution, 1.0 g of methyltrimethoxydecane, and 19.0 g of 3-propenyloxypropyltrimethoxydecane were placed in a flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. 30 g of isopropyl alcohol was added dropwise to an aqueous solution of 5 g of distilled water, 0.3 g of 36% hydrochloric acid and 5 g of isopropyl alcohol at an internal temperature of 70 ° C for 30 minutes, and the reaction was carried out for 3 hours. After cooling to room temperature, 500 3 g of adsorbent Qiwa was added and stirred for 15 minutes to neutralize. After filtration and concentration, 44.0 g of an alkali-soluble compound of sesquioxane-containing compound D-3 was obtained. The Mw of the obtained resin was 16,800.

Example 4

Synthesis of alkali-soluble sesquiterpene-containing compound D-4 In a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, propylene hexahydrophthalate 2-propenyloxyethyl ester 4.0 g, 3 was added. - methacrylic acid methoxypropyl trimethoxy decane 4.5 g, dicyclopentanyl methacrylate 23.0 g, β-mercaptopropionic acid 1.3 g, 2,2'-azobisisobutyronitrile 1.3 g, toluene 137 g, After nitrogen purge for 30 minutes, the flask was placed in an oil bath, and polymerization was carried out at an internal temperature of 80 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain a copolymer solution. Next, 100 g of the obtained polymer solution, 7.1 g of methyltrimethoxydecane, and 12.9 g of 3-propenyloxypropyltrimethoxydecane were placed in a flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. 30 g of isopropyl alcohol was added dropwise to an aqueous solution of 5 g of distilled water, 0.3 g of 36% hydrochloric acid and 5 g of isopropyl alcohol at an internal temperature of 70 ° C for 30 minutes, and the reaction was carried out for 3 hours. After cooling to room temperature, 500 3 g of adsorbent Qiwa was added and stirred for 15 minutes to neutralize. After filtration and concentration, 38.0 g of an alkali-soluble compound containing sesquiterpoxide was obtained. The Mw of the obtained resin was 15,300.

Example 5

Synthesis of alkali-soluble compound containing sesquiterpene oxide D-5 9.0 g of hexahydrophthalic acid 2-propenyloxyethyl ester was added to a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. - methacrylic acid methoxypropyl trimethoxy decane 4.7 g, butyl butyl cyclohexyl methacrylate 18 g, β-mercaptopropionic acid 1.3 g, 2,2'-azobisisobutyronitrile 1.3 g, toluene After 137 g of nitrogen purge for 30 minutes, the flask was placed in an oil bath, and polymerization was carried out at an internal temperature of 80 ° C for 5 hours. Thereafter, it was cooled to room temperature to obtain a copolymer solution. Next, 100 g of the obtained polymer solution, 7.1 g of phenyltrimethoxydecane, and 12.9 g of 3-propenyloxypropyltrimethoxydecane were placed in a flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. 30 g of isopropyl alcohol was added dropwise to an aqueous solution of 5 g of distilled water, 0.3 g of 36% hydrochloric acid and 5 g of isopropyl alcohol at an internal temperature of 70 ° C for 30 minutes, and the reaction was carried out for 3 hours. After cooling to room temperature, 500 3 g of adsorbent Qiwa was added and stirred for 15 minutes to neutralize. After filtration, it was concentrated to give 38.0 g of the compound D-5, which was alkali-soluble sesquioxane. The Mw of the obtained resin was 16,600.

Example 6

100 parts by weight of the alkali-soluble sesquiterpene-containing compound D-1 obtained in Example 1, 907 parts by weight of Iruga, and 4 parts by weight of DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.). 0.01 parts by weight of Mecoca 172 was dissolved in propylene glycol monomethyl ether acetate to have a solid concentration of 30% by weight. This solution was filtered through a millimeter-pore filter having a pore size of 0.2 μm to obtain a thermally radiation-linear resin composition.

Example 7

The same procedure as in Example 6 was carried out except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to the alkali-soluble sesquiterpene-containing compound (D-2) obtained in Example 2. To obtain a thermally radioactive linear resin composition.

Example 8

The same procedure as in Example 6 was carried out except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to the alkali-soluble sesquiterpene-containing compound (D-3) obtained in Example 3. To obtain a thermally radioactive linear resin composition.

Example 9

The same procedure as in Example 6 was carried out except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to the alkali-soluble sesquiterpene-containing compound (D-4) obtained in Example 4. To obtain a thermally radioactive linear resin composition.

Example 10

The same procedure as in Example 6 was carried out except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to the alkali-soluble sesquiterpene-containing compound (D-5) obtained in Example 5, To obtain a thermally radioactive linear resin composition.

Comparative example 1

The same procedure as in Example 6 was carried out, except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to phenolic epoxy acrylate C-0011 (manufactured by Nippon Kayaku Co., Ltd.). To obtain a thermally radioactive linear resin composition.

Comparative example 2

The same procedure as in Example 6 except that the alkali-soluble sesquiterpene-containing compound (D-1) was changed to bisphenol A-type epoxy acrylate TCR-1122 (manufactured by Nippon Kayaku Co., Ltd.) To obtain a thermally radioactive linear resin composition.

Evaluation of thermal radiation linear resin composition

The thermally-radioactive linear resin compositions obtained in Examples 6 to 10 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 1.

1. Patterning characteristics of the film The heat-radiating linear resin compositions obtained in Examples 6 to 10 and Comparative Examples 1 and 2 were applied onto a glass substrate using a spin coater, and then subjected to a hot plate at 90 ° C for 120 seconds. Prebaking was carried out to obtain a coating film having a film thickness of about 0.5 μm. Next, a photomask having a predetermined pattern was placed on a glass substrate having a coating film, and a high-pressure mercury lamp of 250 W was used to irradiate ultraviolet rays having a light intensity of 9.5 mW/cm ² at a wavelength of 405 nm to have an energy of 1000 mJ/cm ² . Subsequently, development treatment was carried out at 23 ° C for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide to remove the unexposed portion of the coating film, thereby obtaining a substrate having a pattern composed of a residual film. The evaluation is based on the following criteria. "Corning 7059 (manufactured by Corning)" was used for the glass substrate.

(Pattern shape evaluation) ◎: No change was observed before and after heating. ○: Some slight changes were observed before and after heating. △: There is a considerable change.

2. Light Penetration Rate The coating film obtained by the above prebaking was measured for the spectral transmittance by using a Hitachi spectrophotometer U-2000. The evaluation is based on the following criteria.

○: The minimum penetration rate is 95% or more. ×: The lowest penetration rate is 95% or less.

3. Heat resistance The substrate having the pattern obtained in the above 1 was heated at 230 ° C for 60 minutes, and the pattern state (shape, surface state) was observed, and the thermal deformation of the pattern was observed. The cross-sectional shape of the linear pattern before and after heating was compared.

○: No change was observed before and after heating. ×: A change was observed before and after heating.

4. Heat Discoloration Resistance The substrate having the pattern obtained in the above 1 was heated at 230 ° C for 60 minutes, and the transmittance of the glass substrate was measured at a wavelength of 400 to 700 nm using a spectrophotometer (Hitachi spectrophotometer U-2000). The change in the transmittance is determined by the following equation.

Change in transmittance = [(transmission before heating - transmittance after heating] × 100 (%) ○: change in transmittance is less than 5%. ×: change in transmittance exceeds 5%.

5. Pencil Hardness The coating film obtained by the above prebaking was heated at 230 ° C for 60 minutes, and the obtained cured film was measured for pencil hardness in accordance with the test method of JIS-K-5400. The highest hardness at which the cured film was not damaged when a load of 9.8 N was applied using a pencil hardness tester was defined as pencil hardness.

6. Sensitivity is expressed in terms of hardening at 1000 mJ/cm ² according to gradation (Kodak Photographic Step Tablet No. 2). The larger the number, the higher the sensitivity.

7. Developability The L/S square cross section formed on the tantalum wafer with a line width of 0.5 μm was observed by a scanning electron microscope, and the evaluation criteria were as follows.

○: There is no development residue between the patterns. △: There is a partial development residue between the patterns. ×: There are many development residues between the patterns.

It is understood from Examples 6 to 10 that the heat-radiating linear resin composition using the alkali-soluble sesquiterpene-containing compound of the present invention is particularly excellent in light transmittance, heat resistance, patterning property, and heat discoloration resistance. Further, in terms of developability and sensitivity, it is possible to exhibit better performance than Comparative Example 1 and Comparative Example 2 of the prior art.

Industrial availability

The sesquioxane-containing compound of the present invention is excellent in transparency and heat resistance, and has good sensitivity and resolution, and is suitable as a thermal radiation linearity such as a transparent insulating film formed between a TFT and a transparent electrode. The resin composition is also suitable for display elements such as liquid crystal display elements and plasma display panels (PDPs), and is extremely advantageous for improving the performance of display elements. Further, the production method of the present invention can easily impart alkali solubility, weather resistance, and adhesion to a compound containing sesquiterpene oxide by radical copolymerization of a vinyl monomer followed by co-condensation of a trialkoxysilane. It is extremely advantageous to be able to synthesize a sesquiterpene-containing compound having a desired function, such as properties, miscibility, flame retardancy, photopolymerization and the like.

Claims (14)

A sesquiterpene-containing compound for a transparent insulating film between a TFT and a transparent electrode, which has a (meth) acrylate (A) having a trialkoxycarbenyl group in the molecule and which may have a substituent The (meth) acrylate (B) is copolymerized into the copolymer (I), and the copolymer (I) is co-condensed with a trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule. be made of. A compound containing a sesquiterpene oxide according to claim 1, wherein the (meth) acrylate (B) is selected from the group consisting of a functional group capable of imparting alkali solubility to a compound containing a sesquiterpene oxide. (meth)acrylic acid ester (b), and (meth)acrylic acid having a functional group capable of imparting at least one of heat resistance and weather resistance to a compound containing sesquiterpene oxide as a substituent At least one of the groups consisting of the ester (b-2). A compound containing sesquiterpene oxide according to item 2 of the patent application, wherein the (meth) acrylate (b-1) contains a carboxyl group. The compound containing sesquiterpene oxide according to item 3 of the patent application, wherein the (meth) acrylate (b-1) is 2-(methyl) propylene methoxyethyl phthalate, six 2-(Methyl)propenyloxyethyl hydrogen phthalate, β-carboxyethyl acrylate, ω-carboxypolycaprolactone monoacrylate, or ethylene oxide-modified succinic acid acrylate. A compound containing a sesquiterpene oxide, which copolymerizes a (meth) acrylate (A) having a trialkoxycarbenyl group in a molecule with a (meth) acrylate (B) which may have a substituent Compound (I), which is obtained by co-condensing the copolymer (I) with a trialkoxy decane compound (C') having an ethylenic carbon-carbon double bond in the molecule; The (meth) acrylate (B) is selected from (meth) acrylate (b-1) having a functional group capable of imparting alkali solubility to a compound containing sesquiterpene oxide as a substituent, and At least one of the group consisting of a (meth) acrylate (b-2) having a functional group which imparts at least one of heat resistance and weather resistance to a compound containing sesquiterpene oxide; Acrylate (b-2), which is dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 9-methylpropene oxide Formamidine, or tetrahydrofurfuryl (meth)acrylate. A compound containing a sesquiterpene oxide according to claim 1, wherein the (meth) acrylate (B) is selected from a functional group having an adhesion to a compound containing a sesquiterpene oxide. a (meth)acrylic acid ester (b), a (meth)acrylic acid having a functional group capable of imparting at least one of a miscibility and a hydrophobic property to a compound containing a sesquiterpene oxide as a substituent At least one of the group consisting of the ester (b-4) and the (meth)acrylate (b-5) having a functional group capable of imparting flame retardancy to the compound containing sesquiterpene oxide as a substituent. A compound containing sesquiterpene oxide according to item 1 of the patent application, wherein the trialkoxy decane compound (C') is a (meth) propylene oxime methoxy decane, a vinyl trimethoxy decane, Or p-styrene trimethoxy decane. A compound containing sesquiterpene oxide according to item 1 of the patent application, which is a cage structure. The compound containing a sesquiterpene oxide according to the first aspect of the invention, wherein the amount of the (meth) acrylate (A) component in the copolymer (I) is from 5 to 95% by mass. The compound containing sesquiterpene oxide according to item 1 of the patent application, wherein the copolymer (I) has a weight average molecular weight of from 1,000 to 50,000. A heat radiation linear resin composition characterized by being alkali-soluble and containing a compound containing sesquiterpene oxide of the second aspect of the patent application. The heat radiation linear resin composition of claim 11, which comprises a photopolymerization initiator (E), a crosslinking agent (F), and a surfactant (G). An electronic component or optical component substrate characterized by having a hardened layer of a thermally radiating linear resin composition of claim 11 of the patent application. A method for producing a sesquiterpene-containing compound for a transparent insulating film between a TFT and a transparent electrode, which comprises the following process: (1) having a trialkoxycarbenyl group in the molecule ( The methyl acrylate (A) is copolymerized with the (meth) acrylate (B) which may have a substituent, and (2) the obtained copolymer and the molecule may have an ethyl carbon-carbon double bond. The trialkoxydecane compound (C) is subjected to co-condensation.