Thiourea-containing polymers

Abstract

To provide a thiourea-containing polymer with high hydrogen-bonding capacity obtained by radical copolymerization of a radical-polymerizable monomer and a compound having an allylthiourea structure.SOLUTION: The thiourea-containing polymer is a radical copolymer obtained by radical copolymerization of a radical-polymerizable monomer and a compound having an allylthiourea structure represented by general formula (1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thiourea-containing polymer, and more particularly to a thiourea-containing polymer having high hydrogen bonding ability obtained by radical copolymerization of a compound having an allylthiourea structure and a radically polymerizable monomer. [Background technology]

[0002] The thiourea structure is known to be effective in adsorbing metal ions and improving adhesion to metal films. For example, JP 2015-174878 A (Patent Document 1) discloses a metal adsorbent formed using a polymer alloy containing an ethylene-vinyl alcohol copolymer and a thiourea group-containing amine polymer in which at least a portion of the amino groups have been modified to thiourea groups, and JP 2011-235236 A (Patent Document 2) discloses a metal adsorbent made of a polyallylamine derivative composed of specific repeating units having both an amino group of polyallylamine and a thiourea group in which one hydrogen atom of the amino group of polyallylamine has been substituted with isothiocyanate.

[0003] In addition, due to their unique structure, compounds with thiourea structures are likely to exhibit hydrogen bonds between polymer chains, and it has been pointed out that they may be applicable to a variety of highly functional materials. For example, Yu Yanagisawa and 3 others, "Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking," Science, January 5, 2018, Vol. 359, pp. 72-76 (Non-Patent Document 1), describes an example of application of compounds having a thiourea structure to self-repairing materials such as glass, which returns to its original shape even if broken, by utilizing the high cohesive force of the compounds. It is expected that these compounds will be used in electronic materials with improved functionality, such as mechanical strength, durability, and high adhesion.

[0004] On the other hand, in the field of electronic material applications, materials are often designed mainly based on polymers of radically polymerizable monomers such as acrylic acid esters and methacrylic acid esters. Although the thiourea structure is expected to improve the functionality as described above, there have been no examples of introducing the thiourea structure into a polymer, which is believed to be because it has been thought in the art that it is not easy or difficult to introduce the thiourea structure into a polymer. For example, Japanese Patent No. 5697223 (Patent Document 3) describes that an ultraviolet-curable resin composition containing 100 parts by weight of a (meth)acrylate monomer and / or acrylate oligomer having a (meth)acryloyl group, 0.1 to 50 parts by weight of a silane coupling agent in which an alkoxysilane coupling agent having a specific structure and a (meth)acrylic group-containing silane coupling agent are used in combination in a specific weight ratio, and a photopolymerization initiator, and a coating film thereof has good adhesion to metal films such as copper and silver. Thus, the applications of thiourea-type silane coupling agents are limited to ultraviolet-curable resin compositions and conductive films intended to enhance adhesion to metal films, and no specific and effective polymers have yet been found in which a thiourea structure has been reacted with a radical polymerizable monomer.

[0005] In recent years, there has been a demand for material designs that aim to improve functionality such as mechanical strength, durability, and high adhesion, particularly in applications such as semiconductor encapsulation, adhesion and sealing of electrical and electronic components, and protective potting and coating of electrical and electronic components, and there is a demand for the introduction of thiourea structures into polymers of radical polymerizable monomers. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2015-174878 A [Patent Document 2] JP 2011-235236 A [Patent Document 3] Patent No. 5697223 [Non-Patent Document 1] Yu Yanagisawa and others, “Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking”, Science, January 5, 2018, Volume 359, p.72-76 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a thiourea-containing polymer having high hydrogen bonding ability, which is obtained by radical copolymerization of a compound having an allylthiourea structure with a radically polymerizable monomer. [Means for solving the problem]

[0008] As a result of intensive research to solve the above problems, the inventors of the present invention have found that a thiourea-containing polymer having high hydrogen bonding ability can be obtained by radically copolymerizing a compound having a specific allylthiourea structure with a radically polymerizable monomer, and have thus completed the present invention.

[0009] Thus, according to the present invention, a compound of the general formula (I): [ka]

[0010] [In the formula, R 1 and R 2are each independently a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a group represented by the formula: -XA (wherein X is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms in which an oxygen atom may be present between the carbon bonds of the alkylene group, if possible, or a substituted or unsubstituted cyclic alkylene group having 3 to 12 carbon atoms, and A is a hydrogen atom, an alkylamino group, an ester group, a carboxylic acid group, a vinyl group, a hydroxyl group, or a substituted or unsubstituted aromatic hydrocarbon group). The present invention provides a thiourea-containing polymer, which is a radical copolymer obtained by radically copolymerizing a compound having an allylthiourea structure represented by the following formula (I): Effect of the Invention

[0011] According to the present invention, it is possible to provide a thiourea-containing polymer having high hydrogen bonding ability, which is obtained by radical copolymerization of a compound having an allylthiourea structure and a radically polymerizable monomer. It is believed that the high hydrogen bonding property of the allylthiourea structure, that is, the hydrogen bonding between thiourea groups as shown in the following formula, imparts high toughness to the polymer.

[0012] [ka]

[0013] The thiourea-containing polymer of the present invention is useful for introducing a thiourea structure into polymers obtained by radical polymerization, and in applications such as semiconductor encapsulation materials, adhesion and sealing of electric and electronic components, and protective potting and coating of electric and electronic components, the hydrogen bonding properties of the structure can be utilized to impart functions such as excellent mechanical strength, durability, and high adhesion to polymer materials.

[0014] The thiourea-containing polymer of the present invention exhibits the above-mentioned effects more effectively when any one of the following conditions is satisfied. (1) The compound having an allylthiourea structure is diethylallylthiourea or hydroxyethylallylthiourea. (2) The radical copolymer contains 3 to 40 mol % of thiourea groups. (3) The radical polymerizable monomer is an acrylic acid ester or a methacrylic acid ester. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram showing the 1H-NMR spectrum of the radical copolymer obtained in Example 1. [Diagram 2] FIG. 1 is a diagram showing the 1H-NMR spectrum of the radical copolymer obtained in Example 2. [Diagram 3] FIG. 1 is a diagram showing a 1H-NMR spectrum of the radical copolymer obtained in Example 3. [Figure 4] FIG. 1 is a diagram showing the 1H-NMR spectrum of the radical copolymer obtained in Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The thiourea-containing polymer of the present invention has the general formula (I): [ka]

[0017] [In the formula, R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a group represented by the formula: -XA (wherein X is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms in which an oxygen atom may be present between the carbon bonds of the alkylene group, if possible, or a substituted or unsubstituted cyclic alkylene group having 3 to 12 carbon atoms, and A is a hydrogen atom, an alkylamino group, an ester group, a carboxylic acid group, a vinyl group, a hydroxyl group, or a substituted or unsubstituted aromatic hydrocarbon group). The compound having an allylthiourea structure represented by the following formula (I) is a radical copolymer obtained by radical copolymerization of a compound having an allylthiourea structure represented by the following formula (I) with a radical polymerizable monomer.

[0018] [Compounds with allylthiourea structure] The compound having an allylthiourea structure is represented by the general formula (I). The "aromatic hydrocarbon group" in the general formula (I) is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include phenyl, naphthyl, anthryl, and phenanthryl. These may be substituted with appropriate substituents (e.g., alkyl, alkoxy, halogen).

[0019] The "straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms" in the general formula (I) is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, and branched-chain alkyl groups which are structural isomers thereof. These may be substituted with an appropriate substituent (e.g., alkoxy, halogen).

[0020] In the "straight-chain or branched-chain alkylene group having 1 to 20 carbon atoms in which an oxygen atom may be present between carbon bonds of the alkylene group, if possible," X in the group represented by the formula -XA has 2 to 20 carbon atoms in the case where an oxygen atom is present between carbon bonds of the alkylene group. Therefore, the "straight-chain or branched-chain alkylene group having 2 to 20 carbon atoms in which an oxygen atom is present between the carbon bonds of the alkylene group" is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include diethylene oxide, di(trimethylene) oxide, dipropylene oxide, di(tetramethylene) oxide, di(pentamethylene) oxide, di(hexamethylene) oxide, di(heptamethylene) oxide, di(octamethylene) oxide, di(nonamethylene) oxide, di(decamethylene) oxide, ethylenemethylene oxide, triethylenedioxide, tripropylenedioxide, tri(trimethylene) dioxide, tetraethylenetrioxide, tetrapropylenetrioxide, pentaethylenetetraoxide, and hexaethylenepentoxide, and among these, ethylenemethyleneoxide is more preferable. These may be substituted with appropriate substituents (e.g., alkoxy, halogen).

[0021] The "cyclic alkylene group having 3 to 12 carbon atoms" in X of the group represented by formula -XA is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptalene, and decahydronaphthylene. These may be substituted with an appropriate substituent (e.g., alkoxy, halogen).

[0022] The "alkylamino group" in A of the group represented by formula -XA is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include dimethylamino, diethylamino, and dibutylamino. These may be substituted with appropriate substituents (e.g., alkoxy, halogen).

[0023] The "ester group" for A in the group represented by formula -XA is represented by the formula: -COOR' (wherein R' is the above-mentioned linear or branched alkyl group having 1 to 20 carbon atoms), and is not particularly limited as long as it does not impair the effects of the present invention. For example, an ester group in which A is methyl, ethyl, propyl, or butyl is preferable, and an ester group in which A is butyl is more preferable.

[0024] The "substituted or unsubstituted aromatic hydrocarbon group" in A of the group represented by formula -XA is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include phenyl, naphthyl, anthryl, phenanthryl, biphenylyl, methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, t-butylphenyl, hexylphenyl, heptylphenyl, octylphenyl, dodecylphenyl, xylyl, trimethylphenyl, and cyanophenyl. These may be substituted with an appropriate substituent (e.g., alkoxy, halogen).

[0025] Halogen in the above suitable substituents includes fluorine, chlorine, bromine and iodine.

[0026] In the present invention, examples of the "compound having an allylthiourea structure" represented by general formula (I) include dimethylallylthiourea, diethylallylthiourea, dipropylallylthiourea, dibutylallylthiourea, diisopropylallylthiourea, dihexylallylthiourea, dioctylallylthiourea, dihydroxyethylallylthiourea, dicyclohexylthiourea, diphenylallylthiourea, methylethylallylthiourea, ethylpropylallylthiourea, ethylisopropylallylthiourea, isopropylhexylallylthiourea, methylallylthiourea, ethylallylthiourea, propylallylthiourea, and isopropyl. Allyl thiourea, butyl allyl thiourea, hexyl allyl thiourea, octyl allyl thiourea, decyl allyl thiourea, dodecyl allyl thiourea, 3,3,5-trimethylcyclohexyl allyl thiourea, cyclohexyl allyl thiourea, methylcyclohexyl allyl thiourea, benzyl allyl thiourea, isoamyl allyl thiourea, 2-methylbutyl allyl thiourea, cyclopentyl allyl thiourea, neopentyl allyl thiourea, hydroxyethyl allyl thiourea, methoxypropyl allyl thiourea, ethoxyethyl allyl thiourea, methoxyphenyl allyl thiourea, and hydroxyphenyl allyl thiourea. Among these, the compound having an allylthiourea structure is preferably diethylallylthiourea or hydroxyethylallylthiourea, because of its good solubility in radical polymerizable monomers or polymerization solvents.

[0027] [Radical polymerizable monomer] In the present invention, the "radically polymerizable monomer" can be selected from, for example, substituted or unsubstituted styrene, substituted or unsubstituted alkyl acrylate, substituted or unsubstituted alkyl methacrylate, acrylonitrile, N-alkyl alkyl amide, N-alkyl methacrylamide, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide, isoprene, butadiene, ethylene, vinyl acetate, and combinations thereof.

[0028] Specific examples of radical polymerizable monomers are not particularly limited as long as they do not impair the effects of the present invention. Examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate (including all isomers), butyl methacrylate (including all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate (including all isomers), butyl acrylate (including all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene. , glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (including all isomers), hydroxybutyl methacrylate (including all isomers), N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (including all isomers), hydroxybutyl acrylate (including all isomers), N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-methylacrylamide, N,N-Dimethylacrylamide, Nt-Butylmethacrylamide, Nn-Butylmethacrylamide, N-Methylolacrylamide, N-Ethylolacrylamide, 4-Acrylomorpholine, Vinylbenzoic acid (including all isomers), Diethylaminostyrene (including all isomers), α-Methylvinylbenzoic acid (including all isomers), Diethylaminoα-Methylstyrene (including all isomers), p-Vinylbenzenesulfonic acid, p-Vinylbenzenesulfonic acid sodium salt, Trimethoxysilylpropyl methacrylate, Triethoxysilylpropyl methacrylate, Tributoxysilylpropyl methacrylate acrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, butadiene, isoprene, chloroprene, ethylene, vinyl acetate, and combinations thereof.

[0029] The radically polymerizable monomers preferred in the present invention are selected from substituted or unsubstituted alkyl acrylates, substituted or unsubstituted alkyl methacrylates, and combinations thereof. In the present invention, the radical polymerizable monomer is preferably an acrylic acid ester or a methacrylic acid ester in terms of compatibility with the compound having an allylthiourea structure.

[0030] In the present invention, as the "radically polymerizable monomer", a polyfunctional radically polymerizable monomer may be used. Specific examples of the polyfunctional radical polymerization monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, phenyl Examples of suitable acrylates include, but are not limited to, glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and combinations thereof.

[0031] [Radical copolymerization] The thiourea-containing polymer of the present invention can be obtained by known radical copolymerization of a compound having an allylthiourea structure represented by general formula (I) and a radically polymerizable monomer using a polymerization initiator. Polymerization conditions such as temperature, time, atmosphere, and pressure may be appropriately determined depending on the materials used.

[0032] (Raw material molar ratio of radical polymerizable monomer and compound having an allylthiourea structure) The molar ratio of the radical polymerizable monomer (raw material 1) and the compound having an allylthiourea structure (raw material 2) may be appropriately set depending on the raw materials used, the radical copolymer to be obtained, and the like. For example, the molar ratio of raw material 1 / raw material 2 is 95 / 5 to 5 / 95, and preferably 80 / 20 to 20 / 80.

[0033] (Polymerization initiator) The polymerization initiator is not particularly limited, and various known polymerization initiators can be used. Preferably, a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator) is used.

[0034] Examples of the photopolymerization initiator or photoradical generator include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether); acetophenones (acetophenone, p-dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, etc.) non, 1-hydroxycyclohexylphenyl ketone, etc.); propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc.); butyrylphenones [1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one, etc.];

[0035] Aminoacetophenones [2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenyl propan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, etc.;

[0036] Benzophenones (benzophenone, N,N'-bis(dimethylamino)benzophenone (Michler's ketone), 3,3-dimethyl-4-methoxybenzophenone, etc.); Ketals (acetophenone dimethyl ketal, benzil dimethyl ketal, etc.); Thioxanthenes (thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, etc.); Anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, etc.) , 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.;(thio)xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.);acridines (1,3-bis-(9-acridinyl)propane, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, etc.); Examples of the photopolymerization initiator include triazines (2,4,6-tris(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, etc.); sulfides (benzyl diphenyl sulfide, etc.); acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.); titanocene photopolymerization initiators; and oxime esters. These photopolymerization initiators may be used alone or in combination of two or more.

[0037] Examples of the thermal polymerization initiator include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxides (lauroyl peroxide, etc.), diaroyl peroxides (benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peroxyesters [percarboxylate alkyl esters such as t-butyl peracetate, t-butyl peroxyoctoate, and t-butyl peroxybenzoate, etc.], ketone peroxides, peroxycarbonates, and peroxyketals, and other organic peroxides, azonitrile compounds [2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2 azo compounds such as 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), azobisbutyronitrile, etc., azoamide compounds {2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, etc.}, azoamidine compounds {2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, etc.}, azoalkane compounds [2,2'-azobis(2,4,4-trimethylpentane), 4,4'-azobis(4-cyanopentanoic acid), etc.], and azo compounds having an oxime skeleton [2,2'-azobis(2-methylpropionamide oxime), etc.]. The thermal polymerization initiators may be used alone or in combination of two or more kinds.

[0038] (solvent) The radical copolymerization may be carried out in a solvent. Examples of the solvent include alcohol-based solvents (alkyl alcohols such as ethanol, propanol, isopropanol, butanol, and isobutanol, glycols such as ethylene glycol and propylene glycol, etc.), hydrocarbon-based solvents (aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, etc.), halogenated hydrocarbon-based solvents (methylene chloride, chloroform, etc.), ether-based solvents (chain ethers such as dimethyl ether and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, etc.), ester-based solvents (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketone-based solvents (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc.), cellosolve-based solvents (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.),

[0039] Examples of organic solvents include carbitol-based solvents (methyl carbitol, ethyl carbitol, butyl carbitol, etc.), propylene glycol monoalkyl ether-based solvents (propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, etc.), amide-based solvents (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxide-based solvents (dimethyl sulfoxide, etc.), nitrile-based solvents (acetonitrile, benzonitrile, etc.), and N-methylpyrrolidone. The organic solvents can be used alone or as a mixed solvent.

[0040] (Molar ratio of radically polymerizable monomer component to compound component having an allylthiourea structure in the radical copolymer) The molar ratio of the radically polymerizable monomer component (raw material 1 component) to the compound component having an allylthiourea structure (raw material 2 component) reflects the molar ratio of the raw materials before radical copolymerization. For example, the molar ratio of raw material 1 / raw material 2 is 95 / 5 to 5 / 95, and preferably 80 / 20 to 20 / 80.

[0041] (Number average molecular weight Mn, mass average molecular weight Mw, and their ratio Mw / Mn) The number average molecular weight Mn and mass average molecular weight Mw of the radical copolymer may be appropriately set by material design taking into consideration the physical properties of the copolymer to be obtained, and are, for example, about 500 to 100,000 and about 1,000 to 200,000, respectively, with the ratio Mw / Mn being about 1.0 to 3.0.

[0042] (Glass transition temperature: °C) The glass transition temperature Tg (°C) of the radical copolymer may be appropriately set by material design taking into consideration the physical properties of the copolymer to be obtained, and is, for example, about -40 to 100°C.

[0043] (5% mass reduction temperature: ℃) The 5% mass loss temperature (°C) of the radical copolymer may be appropriately set by material design taking into consideration the physical properties of the copolymer to be obtained, and is, for example, about 200 to 300°C.

[0044] (Thiourea group content) In the present invention, the radical copolymer preferably contains 3 to 40 mol % of thiourea groups in terms of the expression of characteristics through hydrogen bonds. If the thiourea group content is less than 3 mol %, the effect of hydrogen bonding on the material properties may be weak, whereas if the thiourea group content is more than 40 mol %, the properties derived from the radical polymerizable monomer may be impaired. The content of the thiourea group is preferably 15 to 35 mol %, and more preferably 20 to 30 mol %.

[0045] [Application] The thiourea-containing polymer of the present invention is useful for introducing a thiourea structure into polymers obtained by radical polymerization, and in applications such as semiconductor encapsulation materials, adhesion and sealing of electric and electronic components, and protective potting and coating of electric and electronic components, the hydrogen bonding properties of the structure can be utilized to impart functions such as excellent mechanical strength, durability, and high adhesion to polymer materials.

[0046] [Composition] The composition containing the thiourea-containing polymer of the present invention used for various applications may contain various additives as necessary within the range that does not impair the effects of the present invention. (Additives) Examples of additives include thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), defoamers, coatability improvers, thickeners, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, surfactants, dissolution promoters, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, and dispersion aids. These may be used alone or in combination of two or more. EXAMPLES

[0047] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0048] [Example 1] Copolymerization of butyl acrylate and diethylallylthiourea-1 Butyl acrylate (25.6 g, 200 mmol), diethylallylthiourea (8.6 g, 50 mmol), azobisbutyronitrile (2.1 g, 12.8 mmol) as a radical reaction initiator, and 45 g of isopropanol as a solvent were placed in a 100 mL flask equipped with a reflux condenser, a thermometer, and a stirrer, and the mixture was heated at 70°C for 4 hours under a nitrogen atmosphere to carry out polymerization. The resulting reaction mixture was purified by reprecipitation using a methanol / water mixed liquid (3 / 2 v / v), yielding 21.3 g of a butyl acrylate / diethylallylthiourea copolymer. 1The obtained copolymer was confirmed to be the desired copolymer by 1 H-NMR measurement. The obtained polymer had a number average molecular weight of 8,000, a mass average molecular weight of 17,300, a glass transition temperature of -38°C, a 5% mass loss temperature of 251°C, and the thiourea content in the copolymer was 11 mol%.

[0049] 1 The H-NMR measurement results are shown below. 1H-NMR (400MHz, deuterated chloroform) δ (ppm): 0.93 (3H, CH2-C H 3), 1.22(6H,N-CH2-C H 3), 2.40(2H,C H ), 3.69(4H,NC H 2), 4.05(2H,OC H 2), 6.13(1H,N H )

[0050] [Example 2] Copolymerization of butyl acrylate and diethylallylthiourea-2 Polymerization was carried out in the same manner as in Example 1 except that butyl acrylate (19.2 g, 150 mmol) and diethylallylthiourea (17.2 g, 100 mmol) were used, to obtain 23.5 g of a butyl acrylate / diethylallylthiourea copolymer. 1 The obtained copolymer was confirmed to be the desired copolymer by 1 H-NMR measurement. The resulting copolymer had a number average molecular weight of 5,000, a mass average molecular weight of 12,700, a glass transition temperature of -23°C, a 5% mass loss temperature of 233°C, and the thiourea content in the copolymer was 22 mol %.

[0051] 1 The H-NMR measurement results are shown below. 1H-NMR (400MHz, deuterated chloroform) δ (ppm): 0.94 (3H, CH2-C H 3), 1.22(6H,N-CH2-C H 3), 2.29(2H,C H ), 3.69(4H,NC H2), 4.05(2H,OC H 2), 6.15(1H,N H )

[0052] [Example 3] Copolymerization of butyl acrylate and diethylallylthiourea-3 Polymerization was carried out in the same manner as in Example 1 except that butyl acrylate (12.8 g, 100 mmol) and diethylallylthiourea (25.8 g, 150 mmol) were used, to obtain 14.7 g of a butyl acrylate / diethylallylthiourea copolymer. 1 The obtained copolymer was confirmed to be the desired copolymer by 1 H-NMR measurement. The resulting copolymer had a number average molecular weight of 6,900, a mass average molecular weight of 11,800, a glass transition temperature of -2°C, a 5% mass loss temperature of 214°C, and the thiourea content in the copolymer was 29 mol %.

[0053] 1 The H-NMR measurement results are shown below. 1H-NMR (400MHz, deuterated chloroform) δ (ppm): 0.93 (3H, CH2-C H 3), 1.22(6H,N-CH2-C H 3), 2.27(2H,C H ), 3.69(4H,NC H 2), 4.03(2H,OC H 2), 6.14(1H,N H )

[0054] [Example 4] Copolymerization of butyl acrylate and diethylallylthiourea-4 Polymerization was carried out in the same manner as in Example 1 except that butyl acrylate (6.42 g, 50 mmol) and diethylallylthiourea (34.5 g, 200 mmol) were used, to obtain 7.84 g of a butyl acrylate / diethylallylthiourea copolymer. 1 The obtained copolymer was confirmed to be the desired copolymer by 1 H-NMR measurement. The resulting copolymer had a number average molecular weight of 2,500, a mass average molecular weight of 5,700, a glass transition temperature of 15° C. and a 5% mass loss temperature of 220° C., and the thiourea content in the copolymer was 38 mol %.

[0055] 1 The H-NMR measurement results are shown below. 1H-NMR (400MHz, deuterated chloroform) δ (ppm): 0.93 (3H, CH2-C H 3), 1.22(6H,N-CH2-C H 3), 2.27(2H,C H ), 3.74(4H,NC H 2), 4.01(2H,OC H 2), 6.14(1H,N H )

[0056] [Example 5] Copolymerization of butyl acrylate and hydroxyethylallylthiourea Polymerization was carried out in the same manner as in Example 1 except that butyl acrylate (25.6 g, 200 mmol) and hydroxyethylallylthiourea (8.02 g, 50 mmol) were used, to obtain 24.6 g of a butyl acrylate / diethylallylthiourea copolymer. The copolymer obtained had a number average molecular weight of 7,300, a mass average molecular weight of 17,300, a glass transition temperature of -42°C, and a 5% mass loss temperature of 230°C. The thiourea content in the copolymer was estimated to be 8 mol% by GC and LC analyses. Thus, the GC and LC analyses confirmed that the obtained copolymer was the desired copolymer.

[0057] The results of GC and LC analysis are shown. Using the calibration curve, the conversion of butyl acrylate was estimated to be 99.1 wt% from the GC area value of butyl acrylate 466734 and the GC area value of anisole 519425. The amount of butyl acrylate in the copolymer was estimated to be 198 mmol from the amount of butyl acrylate charged (25.6 g (200 mmol)) and the conversion. Similarly, using the calibration curve, the conversion of hydroxyethyl allyl thiourea was estimated to be 34.5 wt% from the LC area value of hydroxyethyl allyl thiourea 1301112 and the LC area value of anisole 266859. The amount of hydroxyethyl allyl thiourea in the copolymer was estimated to be 17 mmol from the amount of charge (8.02 g (50 mmol) and the conversion. The molar ratio of the copolymer was estimated to be 92:8 from butyl acrylate 198 mmol and hydroxyethyl allyl thiourea 17 mmol, and the thiourea content in the copolymer was estimated to be 8 mol%.

[0058] [Example 6] Copolymerization of methyl methacrylate and hydroxyethylallylthiourea Polymerization was carried out in the same manner as in Example 1 except that methyl methacrylate (20.1 g, 200 mmol) and hydroxyethyl allyl thiourea (8.02 g, 50 mmol) were used, to obtain 11.0 g of a methyl methacrylate / hydroxyethyl allyl thiourea copolymer. The copolymer obtained had a number average molecular weight of 15,500, a mass average molecular weight of 23,500, a glass transition temperature of 98°C and a 5% mass loss temperature of 220°C. The thiourea content in the copolymer was estimated to be 3 mol% by GC and LC analyses. Thus, the GC and LC analyses confirmed that the obtained copolymer was the desired copolymer.

[0059] The results of GC and LC analysis are shown. Using the calibration curve, the conversion of methyl methacrylate was estimated to be 97.3 wt% from the GC area value of 856752 for methyl methacrylate and 1015303 for anisole, and the amount of methyl methacrylate in the copolymer was estimated to be 188 mmol from the amount of methyl methacrylate charged (20.1 g, 200 mmol) and the conversion. Similarly, using the calibration curve, the conversion of hydroxyethyl allyl thiourea was estimated to be 11.4 wt% from the LC area value of 426647 for hydroxyethyl allyl thiourea and LC area value of anisole (74566), and the amount of hydroxyethyl allyl thiourea in the copolymer was estimated to be 5.7 mmol from the amount of 8.02 g (50 mmol) and the conversion. The molar ratio of the copolymer was estimated to be 97:3 from 188 mmol of methyl methacrylate and 5.7 mmol of hydroxyethylallylthiourea, and the thiourea content in the copolymer was estimated to be 3 mol%.

[0060] [Evaluation method] The physical properties of the copolymers and cured products obtained in the examples were measured and evaluated by the following methods. (1)1H-NMR measurement 1 The 1 H-NMR measurements were performed using an FT NMR device (Model: JNM-ECS400, manufactured by JEOL RESONANCE Co., Ltd.) using deuterated chloroform as a solvent and tetramethylsilane (TMS) as a standard substance.

[0061] (2) Differential scanning calorimetry Differential scanning calorimetry was performed using a differential scanning calorimeter (Seiko Instruments Inc. (now Hitachi High-Tech Science Corporation), model: DSC7020) in an aluminum pan in a nitrogen stream at a temperature increase rate of 10°C / min from -80°C to 100°C, and the glass transition temperature Tg (°C) was measured.

[0062] (3) Thermogravimetric (thermal mass) measurement Thermogravimetry was performed using a simultaneous thermogravimetry and differential thermal analyzer (Model: TG / DTA6300, manufactured by Seiko Instruments Inc. (currently Hitachi High-Tech Science Corporation)) and an aluminum pan, with the temperature increased at a rate of 10°C / min in an air flow of 100 mL / min. The temperature at which the mass of each sample (compound) decreased by 5% was defined as the 5% mass loss temperature (°C), which was used as an index of the thermal decomposition temperature.

[0063] (4) Molecular weight measurement The molecular weight was measured by size exclusion chromatography (SEC measurement) using a high performance liquid chromatograph (Shimadzu Corporation, model: Prominence LC-20A). A SEC column (Tosoh Corporation, model: TSKgel MultiporeHxl-M) was used, and measurements were performed at a flow rate of 1 ml / min and a column oven temperature of 40°C using tetrahydrofuran (THF) as the eluent. The molecular weight was measured using TSKgel standard polystyrene.

[0064] (5) Gas chromatography (GC) measurement A gas chromatography apparatus (Shimadzu Corporation, model: GC-2014) was used, and measurements were performed under the following conditions: column HP-1 10 m, inner diameter 0.530 mm, film thickness 2.65 μm, oven temperature 80°C for 1 minute, heated to 300°C at 10°C / min, held at 300°C for 5 minutes, injection temperature 280°C, detector hydrogen flame ionization detector, detector temperature 300°C. The polymerization conversion rates of butyl acrylate and methyl methacrylate were estimated by the internal standard analysis method, and the copolymer composition was estimated based on the results. Anisole was used as the internal standard substance, and the calibration curve for butyl acrylate was (GC area value of butyl acrylate / GC area value of anisole) = 0.78 x (mass of butyl acrylate / mass of anisole), and the calibration curve for methyl methacrylate was (GC area value of methyl methacrylate / GC area value of anisole) = 1.05 x (mass of methyl methacrylate / mass of anisole).

[0065] (6) Liquid chromatography (LC) measurement LC measurements were performed using a high-performance liquid chromatograph (Shimadzu Corporation, model: Prominence LC-20A) and an LC column (Tosoh Corporation, model: TSKgel ODS-100Z 5 μm) with an acetonitrile / water mixture (60 / 40 v / v) as the eluent at a flow rate of 1 ml / min, a column oven temperature of 40°C, and a UV detector at 220 nm. The polymerization conversion of diethylallylthiourea or hydroxyethylallylthiourea was estimated by internal standard analysis, and the copolymer composition was estimated based on the estimated conversion. Anisole was used as the internal standard substance. The calibration curve for diethylallylthiourea was (LC area value of diethylallylthiourea / LC area value of anisole) = 1.52 × (mass of diethylallylthiourea / mass of anisole), and the calibration curve for hydroxyethylallylthiourea was (LC area value of hydroxyethylallylthiourea / LC area value of anisole) = 1.73 × (mass of hydroxyethylallylthiourea / mass of anisole).

[0066] The results are shown in Table 1 together with the monomer components of the copolymer, their ratios, and the thiourea group content.

[0067] [Table 1]

[0068] The results in Table 1 reveal the following: Looking at the thiourea group content and glass transition temperature of the copolymers of Examples 1 to 4, as the thiourea group content increases, the glass transition temperature rises due to the formation of hydrogen bonds. By utilizing this hydrogen bonding ability while maintaining the properties of acrylic, it is expected that polymer materials with excellent mechanical strength, durability, high adhesion, etc. can be provided for applications such as semiconductor encapsulation materials, adhesion and sealing of electrical and electronic components, and protective potting and coating of electrical and electronic components.

Claims

1. General formula (1): 【Chemistry 1】 [In the formula, R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a group represented by the formula: -X-A (wherein X is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms in which an oxygen atom may be present between the carbon bonds of the alkylene group, if possible, or a substituted or unsubstituted cyclic alkylene group having 3 to 12 carbon atoms, and A is a hydrogen atom, an alkylamino group, an ester group, a carboxylic acid group, a vinyl group, a hydroxyl group, or a substituted or unsubstituted aromatic hydrocarbon group). and a radical polymerizable monomer, The thiourea-containing polymer, wherein the radical polymerizable monomer is an acrylic acid ester or a methacrylic acid ester.

2. 2. The thiourea-containing polymer according to claim 1, wherein the compound having an allylthiourea structure is diethylallylthiourea or hydroxyethylallylthiourea.

3. 3. The thiourea-containing polymer according to claim 1, wherein the radical copolymer contains 3 to 40 mol % of thiourea groups.

4. A thiourea-containing polymer described in any one of claims 1 to 3, wherein the acrylic acid ester is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, benzyl acrylate or phenyl acrylate, and the methacrylic acid ester is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, benzyl methacrylate or phenyl methacrylate.

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