JP7563099B2 - Composition, thermosetting composition and cured product thereof, and method for producing the cured product - Google Patents

Description

The present disclosure relates to a composition, a thermosetting composition and a cured product thereof, and a method for producing the cured product.

Photosoftening compositions that are softened by irradiation with light are used in a variety of applications. For example, Patent Document 1 discloses an image forming apparatus equipped with a recording member having a photosoftening resin made of a photosoftening resin composition.

Japanese Patent Application Publication No. 11-190883

One aspect of the present invention aims to provide a composition that can be softened and then hardened by irradiation with light.

One aspect of the present invention relates to a composition containing a compound having a hydroxy group and a disulfide bond, a photoradical generator, and a blocked isocyanate compound.

Since such a composition contains a compound having a hydroxy group and a disulfide bond, a photoradical generator, and a blocked isocyanate compound, it can be softened by irradiation with light and then cured.

In the above composition, the compound having a hydroxy group and a disulfide bond may include at least one selected from the group consisting of a reaction product of a compound having a disulfide bond and a thiol group with a compound having a hydroxy group and a (meth)acryloyl group, a reaction product of a compound having a disulfide bond and a thiol group with a compound having an epoxy group, and a reaction product of a compound having a disulfide bond and a carboxy group with a compound having an epoxy group.

The composition may be used to form a pattern film. The composition may be used as an adhesive.

Another aspect of the present invention relates to a method for producing a cured product, comprising the steps of irradiating the composition with light to soften the composition, thereby forming a softened product of the composition, and curing the softened product by heating to form a cured product.

Another aspect of the present invention relates to a thermosetting composition containing a photoreaction product of a compound having a hydroxy group and a disulfide bond by a photoradical generator, and a blocked isocyanate compound. Another aspect of the present invention relates to a cured product of the thermosetting composition.

Another aspect of the present invention relates to a method for producing a cured product, comprising the step of curing the thermosetting composition by heating to form a cured product.

According to one aspect of the present invention, it is possible to provide a composition that can be softened and then cured by irradiation with light. According to one aspect of the present invention, it is possible to provide a method for producing a cured product using the above composition. According to one aspect of the present invention, it is possible to provide a thermosetting composition using the above composition, a cured product thereof, and a method for producing the cured product.

The following describes in detail the embodiments of the present invention. However, the present invention is not limited to the following embodiments.

In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. In addition, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively.

In addition, in this specification, the content of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. Furthermore, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more types.

In addition, in the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of the numerical range of another stage. In addition, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. A (meth)acryloyl group means an acryloyl group or a methacryloyl group. (Meth)acrylic acid means acrylic acid or methacrylic acid. (Meth)acrylate means an acrylate or the corresponding methacrylate.

The composition of one embodiment contains a compound having a hydroxy group and a disulfide bond (hereinafter also referred to as "component (A)"), a photoradical generator (hereinafter also referred to as "component (B)"), and a blocked isocyanate compound (hereinafter also referred to as "component (C)"). The composition may be in a solid form such as a membrane (film) or block. There are no particular limitations on the method for forming the membrane (film) or block, and known methods can be used.

Component (A): Compound Having a Hydroxy Group and a Disulfide Bond Component (A) is not particularly limited, and may be, for example, a high molecular weight component such as a polymer or oligomer. Component (A) may be used alone or in combination of two or more.

Component (A) may have multiple (two or more) hydroxy groups in the molecule. The number of hydroxy groups contained in the molecule of component (A) may be, for example, 1 or more, or 5 or more, and may be 100 or less, or 50 or less.

Component (A) may have multiple (two or more) disulfide bonds (disulfide groups) in the molecule. The number of disulfide bonds contained in the molecule of component (A) may be, for example, one or more, or three or more, and may be 100 or less, or 50 or less.

From the viewpoint of being even easier to soften, component (A) may be, for example, a polymer having a linear molecular chain to which hydroxyl groups are directly bonded and having a disulfide bond (-S-S-) in the molecular chain. The linear molecular chain may contain a linear hydrocarbon group. The linear molecular chain may further contain one or more bonds selected from the group consisting of an ester bond (-C(=O)-O-) and an ether bond (-O-).

The molecular weight or weight average molecular weight of component (A) may be 100 or more or 10,000,000 or more, or 10,000 or less or 1,000,000 or less. The weight average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

The content of component (A) may be 0.5% by mass or more, or 10% by mass or more, and may be 99.5% by mass or less, or 90% by mass or less, based on the total mass of the composition.

The (A) component may include, for example, a copolymer obtained by reacting a compound having a disulfide bond and an active hydrogen group (hereinafter sometimes referred to as "component (A-1)") with a compound having a substituent capable of reacting with a hydroxy group and an active hydrogen group (hereinafter sometimes referred to as "component (A-2a)"), or a compound having an epoxy group (hereinafter sometimes referred to as "component (A-2b)"). It may be a copolymer containing monomer units of component (A-1) and monomer units of component (A-2a) or monomer units of component (A-2b).

The component (A-1) is a compound having a disulfide bond and an active hydrogen group. Examples of the active hydrogen group include a thiol group, a carboxy group, an amino group, and an imino group. The component (A-1) may be a compound having a disulfide bond and a thiol group from the viewpoints of being inexpensive and easily available, and of being easy to improve transparency.

Component (A-1) may have multiple (two or more) active hydrogen groups. The number of active hydrogen groups in component (A-1) may be, for example, 1 to 3, or may be 2.

The molecular weight or weight average molecular weight of component (A-1) may be 100 to 10,000,000, 1,000 to 2,000,000, or 2,500 to 1,000,000. The weight average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

The (A-1) component may be a compound (e.g., a polymer or oligomer) having a linear molecular chain and terminal groups, with disulfide bonds in the molecular chain. In this case, the terminal groups in the (A-1) component may be active hydrogen groups. When the (A-1) component is such a compound, it becomes even easier to form a cured product with excellent photosoftening properties. The molecular chain in the (A-1) component may contain a disulfide bond and a polyether chain, or may be composed of a disulfide bond and a polyether chain.

The component (A-1) may be a compound represented by formula (1): X-(A-S-S) _n1 -A-X. In the formula, X represents an active hydrogen group, and A represents a polyether chain. A plurality of X's and As may be the same or different. n1 represents an integer of 1 or more. n1 may be, for example, 2 or more, or 4 or more, and may be 100 or less, or 50 or less.

The polyether chain represented by A may be, for example, a polyoxyalkylene chain. The polyether chain represented by A may be, for example, a group represented by -A ¹ -O-A ² -O-A ³ -. ^{A 1} to A ³ may each independently be an alkylene group, or an alkylene group having 1 to 2 carbon atoms (for example, a methylene group, an ethylene group). Specific examples of the polyether chain represented by A include, for example, -CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ CH ₂ -.

Examples of the (A-1) component include the Thiokol LP series (dithiols having a disulfide bond, manufactured by Toray Fine Chemicals Co., Ltd.) and 3,3'-dithiodipropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). These (A-1) components may be used alone or in combination of two or more.

The component (A-2a) is a compound having a substituent capable of reacting with a hydroxy group and an active hydrogen group. An example of a substituent capable of reacting with an active hydrogen group is a (meth)acryloyl group. The component (A-2) may be a compound having a hydroxy group and a (meth)acryloyl group from the viewpoints of cheap availability and ease of improving transparency.

The (A-2a) component may have multiple (two or more) substituents capable of reacting with active hydrogen groups. The number of substituents capable of reacting with active hydrogen groups in the (A-2a) component may be, for example, 1 to 3, or may be 2.

Compounds having a hydroxyl group and a (meth)acryloyl group include butanediol monoacrylate, reaction product of butyl glycidyl ether and (meth)acrylic acid (Denacol (registered trademark) DA-151 manufactured by Nagase & Co., Ltd.), 3-chloro-2-hydroxypropyl methacrylate, glycerol monomethacrylate (Blenmar (registered trademark) GLM manufactured by NOF Corp.), glycerol monoacrylate, glycerin dimethacrylate (Blenmar GMR series manufactured by NOF Corp.), glycerol triacrylate (EX-314 manufactured by Nagase Chemtex Corp.), 2-hydroxyethyl acrylate (BHEA manufactured by Nippon Shokubai Co., Ltd.), 2-hydroxyethyl methacrylate (HEMA manufactured by Nippon Shokubai Co., Ltd.), ), 2-hydroxypropyl acrylate (HPA manufactured by Nippon Shokubai), 2-hydroxypropyl methacrylate (HPMA manufactured by Nippon Shokubai), caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate, phenoxyhydroxypropyl acrylate (M-600A manufactured by Kyoeisha Chemical), 2-hydroxy-3-acryloyloxypropyl methacrylate (G-201P manufactured by Kyoeisha Chemical), Kayarad (registered trademark) R-167 manufactured by Nippon Kayaku, triglycerol diacrylate (Epoxy Ester 80MFA manufactured by Kyoeisha Chemical), pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypentane methacrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 4-(2-acryloyloxyethyl-1-yloxy)benzoic acid, 4-(3-acryloyloxy-n-prop-1-yloxy)benzoic acid acryloyloxyethyl-1-yloxy)benzoic acid, 4-(4-acryloyloxy-n-butyl-1-yloxy)benzoic acid, 4-(6-acryloyloxy-n-hexyl-1-yloxy)benzoic acid, 4-(6-acryloyloxy-n-hexyl-1-yloxy)-2-methylbenzoic acid, 4-(6-methacryloyloxy-n-hexyl-1-yloxy)benzoic acid, 4-(10-acryloyloxy-n-decy-1-yloxy)benzoic acid, 2-acryloyloxyethyl acid phosphate, and 2-methacryloyloxyethyl acid phosphate.

The molar ratio of component (A-1) to component (A-2a) may be, for example, 100:10 to 100:300 or 100:50 to 100:200.

A suitable combination of component (A-1) and component (A-2a) is, for example, a combination of a compound having a disulfide bond and a thiol group with a compound having a hydroxyl group and a (meth)acryloyl group.

Component (A-2b) is a compound having an epoxy group. Epoxy resins can be used as component (A-2b).

The (A-2b) component may have multiple (2 or more) epoxy groups. The number of epoxy groups in the (A-2b) component may be, for example, 1 to 3, or may be 2.

The type of epoxy resin is not particularly limited and can be selected according to the desired properties of the composition. Specific examples of epoxy resins include novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) which are obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc., under an acid catalyst; triphenylmethane-type phenolic resins (triphenylmethane-type phenolic resins, etc.) which are obtained by epoxidizing a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc., under an acid catalyst; diphenylmethane-type epoxy resins; copolymer epoxy resins obtained by epoxidizing novolak resins obtained by co-condensing the above-mentioned phenol compounds and naphthol compounds with aldehyde compounds under an acidic catalyst; diphenylmethane-type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenol compounds; sulfur-containing epoxy resins which are diglycidyl ethers of bisphenol S, etc.; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid. glycidylamine-type epoxy resins in which active hydrogen attached to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene-type epoxy resins in which a co-condensed resin of dicyclopentadiene and a phenol compound is epoxidized; alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane in which an olefin bond in a molecule is epoxidized; paraxylylene-modified epoxy resins which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified phenolic resins Terpene-modified epoxy resins are glycidyl ethers of phenol resins; dicyclopentadiene-modified epoxy resins are glycidyl ethers of dicyclopentadiene-modified phenol resins; cyclopentadiene-modified epoxy resins are glycidyl ethers of cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified epoxy resins are glycidyl ethers of polycyclic aromatic ring-modified phenol resins; naphthalene-type epoxy resins are glycidyl ethers of naphthalene ring-containing phenol resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, epoxy resins such as silicone resins and acrylic resins can also be mentioned. These epoxy resins may be used alone or in combination of two or more.

The molar ratio of component (A-1) to component (A-2b) may be, for example, 100:10 to 100:300 or 100:50 to 100:200.

A suitable combination of component (A-1) and component (A-2b) is, for example, a combination of a compound having a disulfide bond and a thiol group with a compound having an epoxy group, or a combination of a compound having a disulfide bond and a carboxy group with a compound having an epoxy group.

When the (A-1) component is reacted with the (A-2a) or (A-2b) component to obtain a copolymer which is the (A) component, the reaction ratio of these components can be appropriately selected based on the functional group and/or substituent equivalent of each component. The reaction of each component may be carried out while heating. The reaction temperature may be, for example, 0 to 200°C, and the reaction time may be, for example, 0.1 to 240 hours.

When reacting the (A-1) component with the (A-2a) or (A-2b) component, a curing catalyst (hereinafter sometimes referred to as the "(A-3) component") may be used as necessary. The (A-3) component can be selected arbitrarily according to the type of functional group of the (A-3) component and the type of substituent of the (A-3) component. When reacting a compound having a thiol group as a functional group as the (A-3) component with a compound having a hydroxyl group and a (meth)acryloyl group as the (A-3) component, the (A-3) component may be, for example, an amine-based curing catalyst.

Examples of amine-based curing catalysts include triethylamine, triethylenediamine (TEDA), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1-isobutyl-2-methylimidazole (IBN).

The content of component (A-3) may be 0.005 to 10 mass%, 0.01 to 5 mass%, or 0.02 to 3 mass%, based on the total mass of components (A-1), (A-2a), and (A-2b).

Component (A) may include a reaction product of component (A-1) and component (A-2a) or component (A-2b). Component (A) may include at least one selected from the group consisting of a reaction product of a compound having a disulfide bond and a thiol group with a compound having a hydroxyl group and a (meth)acryloyl group, a reaction product of a compound having a disulfide bond and a thiol group with a compound having an epoxy group, and a reaction product of a compound having a disulfide bond and a carboxyl group with a compound having an epoxy group, or may be a reaction product of a compound having a disulfide bond and a thiol group with a compound having a hydroxyl group and a (meth)acryloyl group.

Component (B): Photoradical generator Component (B) may be a component that reacts with a thiyl radical generated when the composition is irradiated with light or a component that generates a photoinduced radical. As the photoradical generator, a photoradical polymerization initiator or the like can be used.

Component (B) may, for example, be an intramolecular cleavage type photoradical polymerization initiator, a hydrogen abstraction type photoradical polymerization initiator, etc. Examples of intramolecular cleavage type photoradical polymerization initiators include benzyl ketal-based photoradical polymerization initiators; α-hydroxyacetophenone-based photoradical polymerization initiators; benzoin-based photoradical polymerization initiators; aminoacetophenone-based photoradical polymerization initiators; oxime ketone-based photoradical polymerization initiators; acylphosphine oxide-based photoradical polymerization initiators; titanocene-based photoradical polymerization initiators; thiobenzoic acid S-phenyl polymerization initiators; and high molecular weight derivatives thereof. Examples of hydrogen abstraction type photoradical polymerization initiators include benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, anthraquinone-based photoradical polymerization initiators, etc.

The content of component (B) may be 5 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, and may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, per 100 parts by mass of the compound having a hydroxy group and a disulfide bond.

The content of component (B) may be, for example, 1 to 30 mass % or 4 to 20 mass % based on the total mass of the composition.

Component (C): Blocked Isocyanate Compound Component (C) is a compound having a blocked isocyanate group. A blocked isocyanate group is an isocyanate group blocked with a protecting group. When the blocked isocyanate group is heated, the protecting group (blocking portion) is thermally dissociated and removed to generate an isocyanate group.

Component (C) may be a polyfunctional blocked isocyanate compound having two or more blocked isocyanate groups. Component (C) can be produced, for example, by a method including reacting a compound having an isocyanate group with a blocking agent.

Examples of blocking agents include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. alcohols such as phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol, o-cresol, m-cresol, p-cresol, xylenol, and the like; lactams such as α-pyrrolidone, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, and the like; acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, methyl ethyl ... ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, and other oximes; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, and other pyrazoles; butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzenethiol, and other mercaptans; malonic acid diesters, acetoacetic esters, malonic acid dinitrile, acetylacetone, methylene disulfone, dibenzoylmethane, dipivaloylmethanate, diphenyl ether ... Examples of the blocked isocyanate compound include active methylene compounds such as amines, dibutylamine, diisopropylamine, di-tert-butylamine, di(2-ethylhexyl)amine, dicyclohexylamine, benzylamine, diphenylamine, aniline, and carbazole, imidazoles such as imidazole and 2-ethylimidazole, imines such as methyleneimine, ethyleneimine, polyethyleneimine, and propyleneimine, acid amides such as acetanilide, acrylamide, acetate amide, and dimer acid amide, acid imides such as succinimide, maleimide, and phthalimide, and urea compounds such as urea, thiourea, and ethyleneurea. The blocked isocyanate compound may be an internally blocked type formed by a uretdione bond (dimerization of an isocyanate group).

Examples of commercially available products of component (C) include the following products:

Takenate (registered trademark) B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, B-882N, B-5010, B-7005, B-7030, B-7075 (all manufactured by Mitsui Chemicals, Inc.).

Duranate (registered trademark) ME20-B80S, MF-B60B, MF-B60X, MF-B90B, MF-K60B, MF-K60X, SBN-70D, 17B-60P, 17B-60PX, TPA-B80E, TPA-B80X, E402-B80B, E402-B80T, and K6000 (all manufactured by Asahi Kasei Chemicals Corp.).

Coronate (registered trademark) 2503, 2507, 2512, 2513, 2515, 2520, 2554, BI-301, AP-M, Millionate MS-50 (all manufactured by Tosoh Corporation).

BURNOCK (registered trademark) D-500, D-550, and DB-980K (all manufactured by DIC Corporation).

Sumidur (registered trademark) BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmotherm (registered trademark) 2170, 2265 (all manufactured by Sumika Bayer Urethane Co., Ltd.).

TRIXENE BI-7641, BI-7642, BI-7986, BI-7987, BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7981, BI-7982, BI-7984, BI-7986, BI-7990, BI-7991, BI-7992, BI-7770, BI-7772, BI-7779, DP9C/214 (all manufactured by Baxten Chemicals).

VESTANAT (registered trademark) B1358A, B1358/100, B1370, VESTAGON (registered trademark) B1065, B1400, B1530, BF1320, BF1540 (all manufactured by Evonik Industries).

Examples of blocked isocyanate compounds include homopolymers or copolymers containing a (meth)acrylate having a blocked isocyanate group as a monomer unit. The homopolymer or copolymer can be obtained, for example, by radical polymerization. Here, the copolymer means a polymer obtained by polymerizing two or more types of monomers. The copolymer may be a copolymer obtained by polymerizing two or more types of (meth)acrylates having a blocked isocyanate group, or a copolymer obtained by polymerizing a (meth)acrylate having a blocked isocyanate group and another (meth)acrylate. Examples of commercially available (meth)acrylates having such blocked isocyanate groups include Karenz (registered trademark) MOI-BM, AOI-BM, MOI-BP, AOI-BP, MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, and MOI-OiPr manufactured by Showa Denko K.K.

Component (C) may be used alone or in combination of two or more types.

The equivalent ratio (molar ratio) of the blocked isocyanate groups of component (C) to the hydroxyl groups of component (A) (NCO groups/OH groups) may be, for example, 100:10 to 100:300 or 100:50 to 100:200.

Component (D): Solvent The composition may be used as a varnish of the composition diluted with a solvent (hereinafter also referred to as "component (D)"). Examples of the component (D) include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP). The component (D) may be used alone or in combination of two or more.

The solids content in the varnish, i.e., the total content of the varnish other than the solvent, may be 1% by mass or more and 99% by mass or less, based on the total mass of the varnish.

The composition may further contain other components in addition to the components (A), (B), (C) and (D). The composition may contain additives such as adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy-imparting agents, flame retardants, release agents, surfactants, lubricants and antistatic agents. The total content of the other components may be 0 to 95% by mass, 0.01 to 50% by mass, or 0.1 to 10% by mass based on the total amount of the composition.

The composition can be prepared, for example, by a method including a step of mixing or kneading the components (A), (B), and (C), and, if necessary, the component (D) and/or other components. When a solvent is used in the mixing or kneading step, the method may further include a step of volatilizing the solvent after the mixing or kneading step. Mixing and kneading can be performed by appropriately combining a conventional mixer, a grinding machine, a triple roll mill, a ball mill, a bead mill, or other dispersing machine.

The composition and coating film thereof according to this embodiment have the property that, when irradiated with light, disulfide bonds (-S-S-) in the composition are cleaved, and the compound having the disulfide bond is reduced in molecular weight and softened. Since the softened composition contains a photoreaction product having a hydroxyl group and a blocked isocyanate compound, the softened composition has the property of hardening when heated as a urethane reaction proceeds. The softened composition can also be called a thermosetting composition.

The light in the light irradiation may be appropriately selected depending on the type of photoradical generator, etc. The light in the light irradiation may be, for example, ultraviolet light or visible light. The wavelength of the light in the light irradiation may be 150 to 830 nm. The light irradiation may be performed, for example, using a light irradiation device under conditions of an irradiation amount of 100 mJ/ ^cm2 or more. The irradiation amount means the product of the illuminance and the irradiation time (seconds). In addition, examples of light sources for irradiating ultraviolet light or visible light include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, metal halide lamps, LED lamps, etc. The light irradiation may be performed directly on the composition or through glass or the like.

The composition may be irradiated with light while being heated. The heating conditions can be adjusted as appropriate, for example, depending on the temperature at which the protecting group (blocking portion) of the blocked isocyanate compound is thermally dissociated. The heating temperature during light irradiation may be, for example, 40 to 90°C.

The photoreaction between component (A) and component (B) cleaves the disulfide bond in component (A). This produces a photoreaction product containing a compound having a hydroxyl group. The thermosetting composition according to this embodiment contains a photoreaction product of a compound having a hydroxyl group and a disulfide bond produced by a photoradical generator, and a blocked isocyanate compound. The photoreaction product may contain a compound having a disulfide bond. In other words, not all disulfide bonds in component (A) may be cleaved by the photoreaction between component (A) and component (B). The photoreaction product may have a structure derived from the photoradical generator.

A cured product is formed by curing the thermosetting composition. The cured product is a urethane reaction product resulting from the reaction between hydroxyl groups in the photoreaction product and isocyanate groups generated from the blocked isocyanate compound. The cured product can be produced by a method including a step of curing the thermosetting composition by heating to form a cured product. The cured product formed into a film shape can be used as a cured film. As one embodiment of the method for producing a cured product, a method for producing a cured product is provided that includes a step of irradiating the composition with light to soften the composition to form a softened product of the composition, and a step of curing the softened product by heating to form a cured product.

The heating temperature (curing temperature) at which the composition is softened and then cured may be, for example, a temperature or higher at which the protective group (blocking portion) of the blocked isocyanate compound is thermally dissociated. The curing temperature may be, for example, 100°C or higher, or 140°C or higher, and may be 200°C or lower. The time for which the composition is held at the curing temperature may be, for example, 10 minutes or more, and may be 100 minutes or less.

The composition and coating film thereof according to this embodiment have the property of softening and then hardening after softening, and are therefore expected to have advantageous effects, for example, in terms of shape conformability (such as conformability to steps), penetration, improved wettability, and patterning.

The storage modulus of the composition at 25°C may be 1 kPa or more and 1000 kPa or less from the viewpoint of excellent slight adhesion or non-adhesiveness, viscosity increase, slitting processability, punching processability, and shielding properties.

The storage modulus of the softened composition (thermosetting composition) at 25°C may be 500 kPa or less, or 0.001 kPa or more, from the viewpoint of excellent foldability, moldability, stress resistance, moisture resistance, repairability, etc.

The storage modulus at 25°C of the cured product of the softened composition (cured product of the thermosetting composition) may be 1 kPa or more and 10,000 kPa or less from the viewpoint of excellent adhesion, slitting processability, punching processability, shielding properties, and resistance to various solvents and/or fuel oils, acids, and alkalis. The storage modulus at 25°C of the cured product of the softened composition (cured product of the thermosetting composition) can be adjusted, for example, by controlling the molar ratio of blocked isocyanate groups in component (C) to hydroxyl groups in component (A), etc.

In this specification, the storage modulus at 25°C refers to the value measured by the method described in the Examples.

The composition according to this embodiment can be used, for example, as a photoresist agent for photolithography. The composition according to this embodiment can be patterned by light irradiation (exposure), and furthermore, after light irradiation (exposure), development can be performed, for example, by washing with water. The composition according to this embodiment can be suitably used for forming a pattern film.

The composition according to the present embodiment can be used as an adhesive. The composition according to the present embodiment may be an adhesive. The above-mentioned components can also be used, for example, in the form of an adhesive set. The adhesive set according to the present embodiment includes a first liquid containing the component (A) and a second liquid containing the component (B), and at least one of the first liquid and the second liquid may further contain the component (C). According to the adhesive set, an adhesive composition containing the component (A), the component (B), and the component (C) can be obtained by mixing the first liquid and the second liquid.

The film according to this embodiment includes the composition described above. The film can be produced, for example, by a method including a step of volatilizing a solvent from a liquid composition including components (A), (B), and (C) and a solvent to form a membrane-like film.

The thickness of the film is not particularly limited, but may be, for example, 1 to 1000 μm, 5 to 800 μm, or 10 to 500 μm.

The film according to this embodiment can be used, for example, as an adhesive film. This film has the property of softening and hardening after softening, so that operations such as fine processing and punching can be performed more easily, and advantageous effects such as shape conformability can also be expected. For example, the adhesive film can be adhered by softening at least a portion of it and then hardening it.

[Method of manufacturing patterned film]
The above-mentioned composition can be used to form a patterned film. The patterned film of one embodiment includes a forming step of forming a coating film of the above-mentioned composition, an exposure step of patterning at least a part of the coating film by irradiating it with light, a developing step of developing the patterned coating film, and a curing step of curing the patterned coating film. The developing step may include a step of developing by washing with water.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

A 300 mL four-neck separable flask was connected to a stirring blade, thermocouple, and nitrogen line to prepare a synthesis apparatus. 8.8 g of hydroxyl group-containing diacrylate (KAYARAD R-167, Nippon Kayaku Co., Ltd.), 91.2 g of disulfide bond-containing dithiol (Thiokol LP-55, Toray Fine Chemicals Co., Ltd.), 0.04 g of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 100 g of toluene were charged into the flask and stirred for 6 hours to complete the synthesis. As a result, 200.04 g of varnish containing a compound having a hydroxyl group and a disulfide bond and a resin content (amount of components other than the solvent) of 100.04 g was obtained.

The varnish, photoradical generator (benzil ketal, IGM Resins B.V.), and blocked isocyanate compound (Sumitomo Bayer Urethane Co., Ltd., Sumidur BL3175) were weighed out in the specified amounts in that order and mixed well to obtain a mixture of these.

The mixed liquid was poured into a silicon mold with a cylindrical depression measuring 29 mm in diameter and 12.5 mm in thickness so that the thickness after drying would be 500 μm. The poured mixed liquid was dried at 130°C for 30 minutes to volatilize the solvent. In this way, a film-like test piece measuring 29 mm in diameter and 500 μm in thickness was produced.

The storage modulus of the test specimens was measured before light irradiation, after light irradiation and before heating, or after light irradiation and after heating. The storage modulus was measured using a viscoelasticity measuring device (TA Instruments, DISCOVERY HR-2 rheometer) at a measurement temperature of 25°C, a frequency of 1 Hz, and a strain of 1%.

The light irradiation conditions were as follows: an LED lamp (manufactured by Panasonic Devices SUNX Co., Ltd., product name: Aicure UJ30/ANUJ6186) was used, the wavelength was 365 nm, and the illuminance was 300 mW/cm ² for 60 seconds.

The heating conditions were: from 25°C to 150°C at a rate of 10°C/min, and after reaching 150°C, the temperature was maintained for 20 minutes.

If the storage modulus at 25°C after light irradiation and before heating is lower than that before light irradiation, it is judged to have softening properties. If the storage modulus at 25°C after heating is higher than that before light irradiation and before heating, it is judged to have hardening properties.

As shown in Table 1, it was demonstrated that the compositions of Examples 1 and 2 were softened by light irradiation and then curable.

Claims (9)

A compound having a hydroxy group and a disulfide bond;
A photoradical generator;
A blocked isocyanate compound ,
the compound having a hydroxy group and a disulfide bond has a plurality of hydroxy groups,
The composition , wherein the blocked isocyanate compound is a polyfunctional blocked isocyanate compound having two or more blocked isocyanate groups . The composition according to claim 1, wherein the compound having a hydroxy group and a disulfide bond includes at least one selected from the group consisting of a reaction product of a compound having a disulfide bond and a thiol group with a compound having a hydroxy group and a (meth)acryloyl group, a reaction product of a compound having a disulfide bond and a thiol group with a compound having an epoxy group, and a reaction product of a compound having a disulfide bond and a carboxy group with a compound having an epoxy group. The composition according to claim 1 or 2, which is used to form a pattern film. The composition according to claim 1 or 2, which is used as an adhesive. A step of irradiating the composition according to any one of claims 1 to 4 with light to soften the composition, thereby forming a softened product of the composition;
and curing the softened material by heating to form a cured material. The photoreaction product of a compound having a hydroxyl group and a disulfide bond by a photoradical generator and a blocked isocyanate compound are contained .
the compound having a hydroxy group and a disulfide bond has a plurality of hydroxy groups,
The thermosetting composition, wherein the blocked isocyanate compound is a polyfunctional blocked isocyanate compound having two or more blocked isocyanate groups . The thermosetting composition according to claim 6, wherein the compound having a hydroxy group and a disulfide bond includes at least one selected from the group consisting of a reaction product of a compound having a disulfide bond and a thiol group with a compound having a hydroxy group and a (meth)acryloyl group, a reaction product of a compound having a disulfide bond and a thiol group with a compound having an epoxy group, and a reaction product of a compound having a disulfide bond and a carboxy group with a compound having an epoxy group. A cured product of the thermosetting composition according to claim 6 or 7. A method for producing a cured product, comprising a step of curing the thermosetting composition according to claim 6 or 7 by heating to form a cured product.