WO2020153425A1 - Curable composition and cured film - Google Patents
Curable composition and cured film Download PDFInfo
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- WO2020153425A1 WO2020153425A1 PCT/JP2020/002318 JP2020002318W WO2020153425A1 WO 2020153425 A1 WO2020153425 A1 WO 2020153425A1 JP 2020002318 W JP2020002318 W JP 2020002318W WO 2020153425 A1 WO2020153425 A1 WO 2020153425A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Definitions
- the present invention relates to a curable composition and a cured film.
- composition that polymerizes and cures a polymerizable compound by light irradiation or heating is used in industrial applications such as coating materials, paints, printing inks, adhesives, optical materials, laminate materials for electronic products, electrical insulating materials, and resist materials. Widely used in.
- Patent Document 1 describes a curable composition containing a photopolymerizable compound containing an amine structure.
- curable compositions are required to retain their initial curability even after being stored for a long period of time.
- an object of the present invention is to provide a curable composition and a cured film having excellent curability after aging.
- the present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, a curable composition containing a compound represented by the formula (1) described later in an amount of more than 60.0 mass% in a solid content was found to be aged. It has been found that the curability of is excellent, and the present invention has been completed.
- the present invention is the following [1] to [4].
- [1] A curable composition containing more than 60.0 mass% of a compound represented by the formula (1) described below in the solid content.
- [2] The curable composition according to the above [1], wherein R 3 in the formula (1) is an alkyl group having 4 or less carbon atoms.
- [3] The curable composition according to the above [1] or [2], which contains more than 65.0% by mass of the compound represented by the formula (1) in the solid content.
- [4] A cured film obtained by curing the curable composition according to any one of the above [1] to [3].
- the range represented by “to” in this specification includes both ends of “to”.
- the range represented by “AB” includes A and B.
- the solid content means the components contained in the composition excluding the solvent, and is calculated as the solid content even if the property is liquid.
- the mechanism by which the curable composition of the present invention is excellent in curability after aging is not clear, but it is considered as follows. Since the compound represented by the formula (1) has a urethane moiety and forms a hydrogen bond between the monomers, decomposition by water is unlikely to occur, and decomposition due to reaction between the monomers is unlikely to occur. However, the effect of making this decomposition less likely to occur becomes stronger when the content of the compound represented by formula (1) in the curable composition is somewhat, specifically, more than 60.0% by mass. To do.
- the curable composition of the present invention contains the compound represented by formula (1) in an amount of more than 60.0% by mass in the solid content. ⁇ Compound represented by formula (1)>
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and a methyl group. It is more preferable that there is.
- examples of the alkyl group having 4 or less carbon atoms include methyl group, ethyl group, propyl group (n-propyl group), 1-methylethyl group (isopropyl group), butyl group (n-butyl group), 1-methyl Examples thereof include a propyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), and a 1,1-dimethylethyl group (tert-butyl group).
- R 1 is plural, R 1 may be different or may be the same as each other.
- R 2 is plural, plural R 2 may be the same as or different from each other.
- R 3 represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by the formula (X), and from the viewpoint of coatability and film surface state, More preferably, it is an alkyl group.
- the alkyl group is preferably an alkyl group having 12 or less carbon atoms, more preferably an alkyl group having 4 or less carbon atoms, and further preferably a methyl group.
- the alkyl group may be linear or branched. Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
- alkyl group having 5 to 12 carbon atoms examples include pentyl group (n-pentyl group), 2,2-dimethylpropyl group (neopentyl group), 3-methylbutyl group (isopentyl group), 1-methylbutyl group (sec- Pentyl group), 1-ethylpropyl group (3-pentyl group), 1,1-dimethylpropyl group (tert-pentyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Groups, but are not limited thereto.
- R 5 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a propan-2-yl group. Is more preferable, and a hydrogen atom or a methyl group is further preferable.
- R 1C represents an oxygen atom or —NR 103 —.
- R 103 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a propan-2-yl group. Is more preferable, a hydrogen atom or a methyl group is further preferable, and a hydrogen atom is further preferable.
- R 1C is preferably an oxygen atom (—O—) or —NH—, and more preferably an oxygen atom (—O—).
- L 5 contains a urethane bond and may contain —O— or —NR 301 —, a divalent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 301 -may be included and represents a divalent hydrocarbon group containing an aromatic ring structure.
- R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
- R 1A and R 1B each independently represent an oxygen atom or —NR 101 —, and preferably an oxygen atom.
- R 101 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom. Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
- R 1A is plural, R 1A may be different may be the same as each other.
- R 2A is a plurality, the plurality of R 2A may be different may be the same as each other.
- L 1 contains a urethane bond and may contain —O— or —NR 201 —, an a+1-valent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 201 -may be included and represents an a+1-valent hydrocarbon group containing an aromatic ring structure.
- R 201 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
- L 3 contains a urethane bond and may contain —O— or —NR 301 —, and contains a c+1-valent aliphatic hydrocarbon group containing no ring structure, or contains a urethane bond, —O— or — NR 301 -may be included and represents a c+1-valent hydrocarbon group containing an aromatic ring structure.
- R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
- R 1 , R 2 , R 1A , R 1B , and R 3 have the same meanings as the same symbols in formula (1).
- L 1 and L 3 are independently -(CH 2 ) p -[O-(CH 2 ) q ] r -. It is preferably NH—CO—O—(CH 2 ) s— [O—(CH 2 ) t ] u ⁇ .
- p, q, s, and t each independently represent an integer of 2 to 10, and preferably an integer of 2 to 3.
- r and u each independently represent an integer of 0 to 10, preferably an integer of 0 to 3.
- Specific examples of the compound represented by the formula (1) include compounds represented by any one of the formulas (1-1) to (1-9), but are not limited thereto. Absent.
- the content of the compound represented by the formula (1) in the curable composition of the present invention should be more than 60.0 mass% in the solid content (based on the solid content) of the curable composition of the present invention. Although not particularly limited, it is preferably more than 65.0% by mass, more preferably 80.0% by mass or more, and further preferably 95.0% by mass or more. Although the upper limit is not particularly limited, for example, it is preferably less than 100% by mass, and more preferably 99.9% by mass or less.
- composition for forming a cured film of the present invention in addition to the above-described compound (1), other monomers, surfactants, polymerization initiators, polymerization inhibitors, solvents, etc., as long as they do not impair the effects of the present invention. You may further contain components other than a compound (1).
- ⁇ Other monomers In the curable composition, a commercially available monofunctional monomer and/or polyfunctional monomer is used in combination with the compound represented by the formula (1) for the purpose of adjusting the mechanical properties of the cured film (tensile strength, abrasion resistance, etc.). You may.
- the content of the other monomer in the curable composition is not particularly limited, but is 0.0% by mass relative to the solid content of the curable composition of the present invention. It is preferably less than 40.0% by mass.
- the content of the other monomer in the curable composition is 0.0% by mass with respect to the solid content of the curable composition, which means that the curable composition does not contain the other monomer. ..
- a commercially available surfactant may be added in order to adjust the wettability and leveling property of the curable composition to the substrate.
- the content of the surfactant in the curable composition when the curable composition contains a surfactant is not particularly limited, but is 0.0% by mass based on the solid content of the curable composition of the present invention. It is preferably 3.0% by mass or less.
- the content of the surfactant in the curable composition is 0.0% by mass based on the total mass of the solid content of the curable composition, and the curable composition does not contain the surfactant.
- the polymerization initiator is not particularly limited, for example, a photoradical polymerization initiator, a photopolymerization initiator such as a photocationic polymerization initiator and a photoanionic polymerization initiator, and a thermal radical polymerization initiator and a thermal cationic polymerization initiator.
- a thermal polymerization initiator may be used.
- the content of the polymerization initiator in the curable composition of the present invention when the curable composition of the present invention contains a polymerization initiator is not particularly limited, but with respect to the solid content of the curable composition of the present invention. 0.1 mass% to 10.0 mass% is preferable, 0.5 mass% to 8.0 mass% is more preferable, and 1.0 mass% to 5.0 mass% is preferable. Is more preferable.
- a commercially available polymerization inhibitor may be added to the curable composition in order to improve the storage stability of the compound represented by formula (1) and the curable composition.
- the content of the polymerization inhibitor in the curable composition is not particularly limited, 0.0005 mass% relative to the solid content of the curable composition of the present invention. It is preferably from about 1.0% by mass.
- solvent The solvent is not particularly limited, but alcohols, ketones, or mixed solvents thereof are preferable, and alcohols having 3 or less carbon atoms, ketones having 4 or less carbon atoms, or mixed solvents thereof are more preferable.
- the content of the solvent in the curable composition of the present invention when the curable composition of the present invention contains a solvent is not particularly limited, but is 10.0 with respect to the total mass of the curable composition of the present invention.
- the content is preferably 9% by mass to 95.0% by mass, more preferably 30.0% by mass to 90.0% by mass, and further preferably 50.0% by mass to 80.0% by mass.
- the curable composition of the present invention may further contain other additives, if necessary.
- the additives include tackifiers, chain transfer agents, sensitizing dyes, polymerization inhibition inhibitors, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, silane coupling agents. Agents, fillers, metal powders and pigments.
- the additives are not limited to these. The kind and content of the additive can be appropriately selected.
- the cured film of the present invention is a cured film obtained by curing the curable composition of the present invention described above.
- the method for producing a cured film is not particularly limited, but it is preferable to dispose the curable composition of the present invention on a substrate to form a curable composition film and cure the curable composition film.
- the method of forming the curable composition film on the substrate is not particularly limited, and for example, gravure coater, comma coater, bar coater, knife coater, die coater, roll coater, spin coating, dipping, painting, or the like. There is a method.
- the method for curing the curable composition film is not particularly limited, but irradiation with light or heating is preferable, and irradiation with light is more preferable.
- the heat resistance of the substrate is low, it is preferable to cure it by irradiation with light.
- the light irradiation may be appropriately selected from visible rays, ultraviolet rays, electron beams, gamma rays and the like.
- the substrate is not particularly limited, but examples thereof include a glass substrate and a resin substrate.
- glass substrates include soda-lime glass substrates, borosilicate glass substrates, and quartz glass substrates.
- the shape of the glass substrate is not particularly limited, but a plate shape is preferable.
- the surface of the glass substrate may be coated or may be modified by plasma treatment or the like.
- the resin substrate include a polyester resin substrate, a polyimide resin substrate, an epoxy resin substrate, a polyether resin substrate, and a polystyrene resin substrate.
- the shape of the resin substrate is not particularly limited, but it is preferably a plate shape or a film shape.
- the surface of the resin base material may be coated or may be modified by plasma treatment or the like.
- composition of the present invention is suitable for use in pattern formation using a curing reaction such as photolithography.
- a curing reaction such as photolithography.
- printing applications such as planographic printing plates, flexographic printing plates and UV inkjet inks, and semiconductor resist material applications are preferable.
- the prepared curable composition was stored at 60° C. for 1 month.
- the curable composition after storage may be referred to as a curable composition after aging.
- the curable composition before and after aging was adjusted with a bar coater so that the thickness after drying was 5 ⁇ m, and an easily-adhesive PET (polyethylene terephthalate) film (Cosmoshine A4100, The product was applied onto Toyobo Co., Ltd.; thickness 100 ⁇ m) and dried to form a curable composition film. Then, the curable composition film was irradiated with ultraviolet rays using an ultraviolet exposure device (HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.).
- HMW-680GW an ultraviolet exposure device
- the curability after aging was evaluated in three grades A to C.
- the evaluation results are shown in Table 1.
- TEGDMA triethylene glycol dimethacrylate, compound represented by the following formula; manufactured by Sigma-Aldrich
- Omnirad 2959 manufactured by IGM Resins
- Omnirad 1173 made by IGM Resins
- Minirad is a registered trademark.
- the curable compositions of Examples 1 to 7 had good curability after aging. From the comparison between Example 1 and Example 3 and the comparison between Example 6 and Example 7, the higher the content, the better the evaluation of the curability after aging, regardless of the type of the monomer. Was suggested. Further, it was suggested that the use of the compound (1-1) in which R 3 in the formula (1) has a small number of carbon atoms results in better curability after aging.
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Abstract
The present invention provides a curable composition having excellent curability after passage of time and a cured film. The curable composition according to the present invention includes more than 60.0 mass% of a compound represented by formula (1) in the solids fraction.
Description
本発明は、硬化性組成物および硬化膜に関する。
The present invention relates to a curable composition and a cured film.
光照射または加熱により重合性化合物を重合させて硬化する組成物は、コーティング材、塗料、印刷インク、接着剤、光学材料、電子製品の積層材料、電気絶縁材料、およびレジスト材などの工業的用途に幅広く利用されている。
The composition that polymerizes and cures a polymerizable compound by light irradiation or heating is used in industrial applications such as coating materials, paints, printing inks, adhesives, optical materials, laminate materials for electronic products, electrical insulating materials, and resist materials. Widely used in.
例えば、特許文献１には、アミン構造を含む光重合性化合物を含む硬化性組成物が記載されている。
For example, Patent Document 1 describes a curable composition containing a photopolymerizable compound containing an amine structure.
一方で、硬化性組成物には、長期間保存した後であっても、初期の硬化性を保持することが求められている。
On the other hand, curable compositions are required to retain their initial curability even after being stored for a long period of time.
そこで、本発明は、経時後の硬化性に優れた硬化性組成物および硬化膜を提供することを課題とする。
Therefore, an object of the present invention is to provide a curable composition and a cured film having excellent curability after aging.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、後述する式（１）で表される化合物を固形分中に６０．０質量％超含む硬化性組成物は、経時後の硬化性に優れることを知得し、本発明を完成させた。
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, a curable composition containing a compound represented by the formula (1) described later in an amount of more than 60.0 mass% in a solid content was found to be aged. It has been found that the curability of is excellent, and the present invention has been completed.
すなわち、本発明は以下の［１］～［４］である。
［１］ 後述する式（１）で表される化合物を固形分中に６０．０質量％超含む硬化性組成物。
［２］ 式（１）中のＲ３が炭素数４以下のアルキル基である、上記［１］に記載の硬化性組成物。
［３］ 式（１）で表される化合物を固形分中に６５．０質量％超含む、上記［１］または［２］に記載の硬化性組成物。
［４］ 上記［１］～［３］のいずれか１つに記載の硬化性組成物を硬化して得られる硬化膜。 That is, the present invention is the following [1] to [4].
[1] A curable composition containing more than 60.0 mass% of a compound represented by the formula (1) described below in the solid content.
[2] The curable composition according to the above [1], wherein R 3 in the formula (1) is an alkyl group having 4 or less carbon atoms.
[3] The curable composition according to the above [1] or [2], which contains more than 65.0% by mass of the compound represented by the formula (1) in the solid content.
[4] A cured film obtained by curing the curable composition according to any one of the above [1] to [3].
［１］ 後述する式（１）で表される化合物を固形分中に６０．０質量％超含む硬化性組成物。
［２］ 式（１）中のＲ３が炭素数４以下のアルキル基である、上記［１］に記載の硬化性組成物。
［３］ 式（１）で表される化合物を固形分中に６５．０質量％超含む、上記［１］または［２］に記載の硬化性組成物。
［４］ 上記［１］～［３］のいずれか１つに記載の硬化性組成物を硬化して得られる硬化膜。 That is, the present invention is the following [1] to [4].
[1] A curable composition containing more than 60.0 mass% of a compound represented by the formula (1) described below in the solid content.
[2] The curable composition according to the above [1], wherein R 3 in the formula (1) is an alkyl group having 4 or less carbon atoms.
[3] The curable composition according to the above [1] or [2], which contains more than 65.0% by mass of the compound represented by the formula (1) in the solid content.
[4] A cured film obtained by curing the curable composition according to any one of the above [1] to [3].
本発明によれば、経時後の硬化性に優れた硬化性組成物および硬化膜を提供できる。
According to the present invention, it is possible to provide a curable composition and a cured film that have excellent curability over time.
本明細書において「～」を用いて表される範囲には、「～」の両端を含むものとする。例えば、「Ａ～Ｂ」と表される範囲には、ＡおよびＢを含む。
The range represented by "to" in this specification includes both ends of "to". For example, the range represented by “AB” includes A and B.
本明細書において、固形分とは、溶媒を除いた組成物に含まれる成分を意図し、その性状が液状であっても固形分として計算する。
In the present specification, the solid content means the components contained in the composition excluding the solvent, and is calculated as the solid content even if the property is liquid.
本発明の硬化性組成物が経時後の硬化性に優れるメカニズムは明らかではないが、次のように考えられる。
式（１）で表される化合物はウレタン部位を有しており、モノマー間で水素結合を形成しているため、水による分解が起こりにくく、かつ、モノマー同士が反応することによる分解も起こりにくくなることによるが、この分解を起こりにくくする効果は、硬化性組成物中の式（１）で表される化合物の含有量がある程度、具体的には６０．０質量％超で、より強く発現する。 The mechanism by which the curable composition of the present invention is excellent in curability after aging is not clear, but it is considered as follows.
Since the compound represented by the formula (1) has a urethane moiety and forms a hydrogen bond between the monomers, decomposition by water is unlikely to occur, and decomposition due to reaction between the monomers is unlikely to occur. However, the effect of making this decomposition less likely to occur becomes stronger when the content of the compound represented by formula (1) in the curable composition is somewhat, specifically, more than 60.0% by mass. To do.
式（１）で表される化合物はウレタン部位を有しており、モノマー間で水素結合を形成しているため、水による分解が起こりにくく、かつ、モノマー同士が反応することによる分解も起こりにくくなることによるが、この分解を起こりにくくする効果は、硬化性組成物中の式（１）で表される化合物の含有量がある程度、具体的には６０．０質量％超で、より強く発現する。 The mechanism by which the curable composition of the present invention is excellent in curability after aging is not clear, but it is considered as follows.
Since the compound represented by the formula (1) has a urethane moiety and forms a hydrogen bond between the monomers, decomposition by water is unlikely to occur, and decomposition due to reaction between the monomers is unlikely to occur. However, the effect of making this decomposition less likely to occur becomes stronger when the content of the compound represented by formula (1) in the curable composition is somewhat, specifically, more than 60.0% by mass. To do.
［硬化性組成物］
本発明の硬化性組成物は、式（１）で表される化合物を固形分中に６０．０質量％超含む。
〈式（１）で表される化合物〉 [Curable composition]
The curable composition of the present invention contains the compound represented by formula (1) in an amount of more than 60.0% by mass in the solid content.
<Compound represented by formula (1)>
本発明の硬化性組成物は、式（１）で表される化合物を固形分中に６０．０質量％超含む。
〈式（１）で表される化合物〉 [Curable composition]
The curable composition of the present invention contains the compound represented by formula (1) in an amount of more than 60.0% by mass in the solid content.
<Compound represented by formula (1)>
式（１）中、各記号の意味は以下のとおりである。
Ｒ１およびＲ２は、それぞれ独立に、水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、メチル基であることがさらに好ましい。ここで、炭素数４以下のアルキル基としては、メチル基、エチル基、プロピル基（ｎ－プロピル基）、１－メチルエチル基（イソプロピル基）、ブチル基（ｎ－ブチル基）、１－メチルプロピル基（ｓｅｃ－ブチル基）、２－メチルプロピル基（イソブチル基）、および１，１－ジメチルエチル基（ｔｅｒｔ－ブチル基）が挙げられる。
Ｒ１が複数であるとき、複数のＲ１は互いに同じであってもよいし異なっていてもよい。
Ｒ２が複数であるとき、複数のＲ２は互いに同じであってもよいし異なっていてもよい。 In the formula (1), the meaning of each symbol is as follows.
R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and a methyl group. It is more preferable that there is. Here, examples of the alkyl group having 4 or less carbon atoms include methyl group, ethyl group, propyl group (n-propyl group), 1-methylethyl group (isopropyl group), butyl group (n-butyl group), 1-methyl Examples thereof include a propyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), and a 1,1-dimethylethyl group (tert-butyl group).
When R 1 is plural, R 1 may be different or may be the same as each other.
When R 2 is plural, plural R 2 may be the same as or different from each other.
Ｒ１およびＲ２は、それぞれ独立に、水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、メチル基であることがさらに好ましい。ここで、炭素数４以下のアルキル基としては、メチル基、エチル基、プロピル基（ｎ－プロピル基）、１－メチルエチル基（イソプロピル基）、ブチル基（ｎ－ブチル基）、１－メチルプロピル基（ｓｅｃ－ブチル基）、２－メチルプロピル基（イソブチル基）、および１，１－ジメチルエチル基（ｔｅｒｔ－ブチル基）が挙げられる。
Ｒ１が複数であるとき、複数のＲ１は互いに同じであってもよいし異なっていてもよい。
Ｒ２が複数であるとき、複数のＲ２は互いに同じであってもよいし異なっていてもよい。 In the formula (1), the meaning of each symbol is as follows.
R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and a methyl group. It is more preferable that there is. Here, examples of the alkyl group having 4 or less carbon atoms include methyl group, ethyl group, propyl group (n-propyl group), 1-methylethyl group (isopropyl group), butyl group (n-butyl group), 1-methyl Examples thereof include a propyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), and a 1,1-dimethylethyl group (tert-butyl group).
When R 1 is plural, R 1 may be different or may be the same as each other.
When R 2 is plural, plural R 2 may be the same as or different from each other.
Ｒ３は、水素原子または１価の置換基を表し、水素原子、アルキル基、アリール基、または式（Ｘ）で表される基であることが好ましく、塗布性や膜面状の観点から、アルキル基であることがより好ましい。
R 3 represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by the formula (X), and from the viewpoint of coatability and film surface state, More preferably, it is an alkyl group.
アルキル基は、炭素数１２以下のアルキル基であることが好ましく、炭素数４以下のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。アルキル基は直鎖状であってもよいし、分岐鎖状であってもよい。
炭素数４以下のアルキル基としては、上述したものが挙げられる。
炭素数５～１２のアルキル基としては、例えば、ペンチル基（ｎ－ペンチル基）、２，２－ジメチルプロピル基（ネオペンチル基）、３－メチルブチル基（イソペンチル基）、１－メチルブチル基（ｓｅｃ－ペンチル基）、１－エチルプロピル基（３－ペンチル基）、１，１－ジメチルプロピル基（ｔｅｒｔ－ペンチル基）、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、およびドデシル基が挙げられるが、これらに限定されるものではない。 The alkyl group is preferably an alkyl group having 12 or less carbon atoms, more preferably an alkyl group having 4 or less carbon atoms, and further preferably a methyl group. The alkyl group may be linear or branched.
Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
Examples of the alkyl group having 5 to 12 carbon atoms include pentyl group (n-pentyl group), 2,2-dimethylpropyl group (neopentyl group), 3-methylbutyl group (isopentyl group), 1-methylbutyl group (sec- Pentyl group), 1-ethylpropyl group (3-pentyl group), 1,1-dimethylpropyl group (tert-pentyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Groups, but are not limited thereto.
炭素数４以下のアルキル基としては、上述したものが挙げられる。
炭素数５～１２のアルキル基としては、例えば、ペンチル基（ｎ－ペンチル基）、２，２－ジメチルプロピル基（ネオペンチル基）、３－メチルブチル基（イソペンチル基）、１－メチルブチル基（ｓｅｃ－ペンチル基）、１－エチルプロピル基（３－ペンチル基）、１，１－ジメチルプロピル基（ｔｅｒｔ－ペンチル基）、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、およびドデシル基が挙げられるが、これらに限定されるものではない。 The alkyl group is preferably an alkyl group having 12 or less carbon atoms, more preferably an alkyl group having 4 or less carbon atoms, and further preferably a methyl group. The alkyl group may be linear or branched.
Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
Examples of the alkyl group having 5 to 12 carbon atoms include pentyl group (n-pentyl group), 2,2-dimethylpropyl group (neopentyl group), 3-methylbutyl group (isopentyl group), 1-methylbutyl group (sec- Pentyl group), 1-ethylpropyl group (3-pentyl group), 1,1-dimethylpropyl group (tert-pentyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Groups, but are not limited thereto.
式（Ｘ）中、各記号の意味は以下のとおりである。
Ｒ５は、水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子、メチル基、エチル基、プロピル基、またはプロパン－２－イル基であることがより好ましく、水素原子またはメチル基であることがさらに好ましい。 In formula (X), the meaning of each symbol is as follows.
R 5 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a propan-2-yl group. Is more preferable, and a hydrogen atom or a methyl group is further preferable.
Ｒ５は、水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子、メチル基、エチル基、プロピル基、またはプロパン－２－イル基であることがより好ましく、水素原子またはメチル基であることがさらに好ましい。 In formula (X), the meaning of each symbol is as follows.
R 5 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a propan-2-yl group. Is more preferable, and a hydrogen atom or a methyl group is further preferable.
Ｒ１Ｃは、酸素原子または－ＮＲ１０３－を表す。Ｒ１０３は、水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子、メチル基、エチル基、プロピル基、またはプロパン－２－イル基であることがより好ましく、水素原子またはメチル基であることがさらに好ましく、水素原子であることがいっそう好ましい。Ｒ１Ｃは、酸素原子（－Ｏ－）または－ＮＨ－であることが好ましく、酸素原子（－Ｏ－）であることがより好ましい。
R 1C represents an oxygen atom or —NR 103 —. R 103 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a propan-2-yl group. Is more preferable, a hydrogen atom or a methyl group is further preferable, and a hydrogen atom is further preferable. R 1C is preferably an oxygen atom (—O—) or —NH—, and more preferably an oxygen atom (—O—).
Ｌ５は、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、環構造を含まない２価の脂肪族炭化水素基、または、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、芳香族環構造を含む２価の炭化水素基を表す。
Ｒ３０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 5 contains a urethane bond and may contain —O— or —NR 301 —, a divalent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 301 -may be included and represents a divalent hydrocarbon group containing an aromatic ring structure.
R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Ｒ３０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 5 contains a urethane bond and may contain —O— or —NR 301 —, a divalent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 301 -may be included and represents a divalent hydrocarbon group containing an aromatic ring structure.
R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Ｒ１ＡおよびＲ１Ｂは、それぞれ独立に、酸素原子または－ＮＲ１０１－を表し、酸素原子であることが好ましい。
Ｒ１０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。
炭素数４以下のアルキル基としては、上述したものが挙げられる。
Ｒ１Ａが複数であるとき、複数のＲ１Ａは互いに同じであってもよいし異なっていてもよい。
Ｒ２Ａが複数であるとき、複数のＲ２Ａは互いに同じであってもよいし異なっていてもよい。 R 1A and R 1B each independently represent an oxygen atom or —NR 101 —, and preferably an oxygen atom.
R 101 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
When R 1A is plural, R 1A may be different may be the same as each other.
When R 2A is a plurality, the plurality of R 2A may be different may be the same as each other.
Ｒ１０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。
炭素数４以下のアルキル基としては、上述したものが挙げられる。
Ｒ１Ａが複数であるとき、複数のＲ１Ａは互いに同じであってもよいし異なっていてもよい。
Ｒ２Ａが複数であるとき、複数のＲ２Ａは互いに同じであってもよいし異なっていてもよい。 R 1A and R 1B each independently represent an oxygen atom or —NR 101 —, and preferably an oxygen atom.
R 101 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Examples of the alkyl group having 4 or less carbon atoms include those mentioned above.
When R 1A is plural, R 1A may be different may be the same as each other.
When R 2A is a plurality, the plurality of R 2A may be different may be the same as each other.
Ｌ１は、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ２０１－を含んでいてもよく、環構造を含まないａ＋１価の脂肪族炭化水素基、または、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ２０１－を含んでいてもよく、芳香族環構造を含むａ＋１価の炭化水素基を表す。
Ｒ２０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 1 contains a urethane bond and may contain —O— or —NR 201 —, an a+1-valent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 201 -may be included and represents an a+1-valent hydrocarbon group containing an aromatic ring structure.
R 201 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Ｒ２０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 1 contains a urethane bond and may contain —O— or —NR 201 —, an a+1-valent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 201 -may be included and represents an a+1-valent hydrocarbon group containing an aromatic ring structure.
R 201 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Ｌ３は、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、環構造を含まないｃ＋１価の脂肪族炭化水素基、または、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、芳香族環構造を含むｃ＋１価の炭化水素基を表す。
Ｒ３０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 3 contains a urethane bond and may contain —O— or —NR 301 —, and contains a c+1-valent aliphatic hydrocarbon group containing no ring structure, or contains a urethane bond, —O— or — NR 301 -may be included and represents a c+1-valent hydrocarbon group containing an aromatic ring structure.
R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
Ｒ３０１は水素原子またはアルキル基を表し、水素原子または炭素数４以下のアルキル基であることが好ましく、水素原子またはメチル基であることがより好ましく、水素原子であることがさらに好ましい。 L 3 contains a urethane bond and may contain —O— or —NR 301 —, and contains a c+1-valent aliphatic hydrocarbon group containing no ring structure, or contains a urethane bond, —O— or — NR 301 -may be included and represents a c+1-valent hydrocarbon group containing an aromatic ring structure.
R 301 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
ａおよびｃは、それぞれ独立に、１～３の整数を表し、ａ＝ｃ＝１であることが好ましい。ａ＝ｃ＝１であるとき、式（１）は式（２）と一致する。
“A” and “c” each independently represent an integer of 1 to 3, and preferably a=c=1. When a=c=1, the equation (1) matches the equation (2).
式（２）中、Ｒ１、Ｒ２、Ｒ１Ａ、Ｒ１Ｂ、およびＲ３は、式（１）中の同一の記号と同じ意味である。Ｌ１およびＬ３は、式（１）中の同一の記号のａ＝ｃ＝１であるときと同じ意味である。
In formula (2), R 1 , R 2 , R 1A , R 1B , and R 3 have the same meanings as the same symbols in formula (1). L 1 and L 3 have the same meaning as when a=c=1 of the same symbol in formula (1).
ａ＝ｃ＝１であるときの式（１）、および式（２）において、Ｌ１およびＬ３は、それぞれ独立に、－（ＣＨ２）ｐ－［Ｏ－（ＣＨ２）ｑ］ｒ－ＮＨ－ＣＯ－Ｏ－（ＣＨ２）ｓ－［Ｏ－（ＣＨ２）ｔ］ｕ－であることが好ましい。ここで、ｐ、ｑ、ｓ、およびｔは、それぞれ独立に、２～１０の整数を表し、２～３の整数であることが好ましい。ｒおよびｕは、それぞれ独立に、０～１０の整数を表し、０～３の整数であることが好ましい。
In the formula (1) and the formula (2) when a=c=1, L 1 and L 3 are independently -(CH 2 ) p -[O-(CH 2 ) q ] r -. It is preferably NH—CO—O—(CH 2 ) s— [O—(CH 2 ) t ] u −. Here, p, q, s, and t each independently represent an integer of 2 to 10, and preferably an integer of 2 to 3. r and u each independently represent an integer of 0 to 10, preferably an integer of 0 to 3.
式（１）で表される化合物の具体例としては、式（１－１）～式（１－９）のいずれか１つで表される化合物が挙げられるが、これらに限定されるものではない。
Specific examples of the compound represented by the formula (1) include compounds represented by any one of the formulas (1-1) to (1-9), but are not limited thereto. Absent.
〈式（１）で表される化合物の含有量〉
本発明の硬化性組成物中の式（１）で表される化合物の含有量は、本発明の硬化性組成物の固形分中（固形分に対して）、６０．０質量％超であれば特に限定されないが、６５．０質量％超であることが好ましく、８０．０質量％以上であることがより好ましく、９５．０質量％以上であることがさらに好ましい。上限は特に限定されないが、例えば、１００質量％未満であることが好ましく、９９．９質量％以下であることがより好ましい。 <Content of Compound Represented by Formula (1)>
The content of the compound represented by the formula (1) in the curable composition of the present invention should be more than 60.0 mass% in the solid content (based on the solid content) of the curable composition of the present invention. Although not particularly limited, it is preferably more than 65.0% by mass, more preferably 80.0% by mass or more, and further preferably 95.0% by mass or more. Although the upper limit is not particularly limited, for example, it is preferably less than 100% by mass, and more preferably 99.9% by mass or less.
本発明の硬化性組成物中の式（１）で表される化合物の含有量は、本発明の硬化性組成物の固形分中（固形分に対して）、６０．０質量％超であれば特に限定されないが、６５．０質量％超であることが好ましく、８０．０質量％以上であることがより好ましく、９５．０質量％以上であることがさらに好ましい。上限は特に限定されないが、例えば、１００質量％未満であることが好ましく、９９．９質量％以下であることがより好ましい。 <Content of Compound Represented by Formula (1)>
The content of the compound represented by the formula (1) in the curable composition of the present invention should be more than 60.0 mass% in the solid content (based on the solid content) of the curable composition of the present invention. Although not particularly limited, it is preferably more than 65.0% by mass, more preferably 80.0% by mass or more, and further preferably 95.0% by mass or more. Although the upper limit is not particularly limited, for example, it is preferably less than 100% by mass, and more preferably 99.9% by mass or less.
《化合物（１）の合成方法》
化合物（１）は、従来公知の方法によって、容易に合成することができる。 <<Synthesis Method of Compound (1)>>
The compound (1) can be easily synthesized by a conventionally known method.
化合物（１）は、従来公知の方法によって、容易に合成することができる。 <<Synthesis Method of Compound (1)>>
The compound (1) can be easily synthesized by a conventionally known method.
〈式（１）で表される化合物以外の成分〉
本発明の硬化膜形成用組成物は、本発明の作用効果を妨げない限り、上述した化合物（１）に加えて、他のモノマー、界面活性剤、重合開始剤、重合禁止剤および溶媒など、化合物（１）以外の成分をさらに含んでもよい。 <Components Other than the Compound Represented by Formula (1)>
The composition for forming a cured film of the present invention, in addition to the above-described compound (1), other monomers, surfactants, polymerization initiators, polymerization inhibitors, solvents, etc., as long as they do not impair the effects of the present invention. You may further contain components other than a compound (1).
本発明の硬化膜形成用組成物は、本発明の作用効果を妨げない限り、上述した化合物（１）に加えて、他のモノマー、界面活性剤、重合開始剤、重合禁止剤および溶媒など、化合物（１）以外の成分をさらに含んでもよい。 <Components Other than the Compound Represented by Formula (1)>
The composition for forming a cured film of the present invention, in addition to the above-described compound (1), other monomers, surfactants, polymerization initiators, polymerization inhibitors, solvents, etc., as long as they do not impair the effects of the present invention. You may further contain components other than a compound (1).
《他のモノマー》
硬化性組成物は、硬化膜の力学物性（引張強度や耐摩耗性など）を調整する目的で、市販の単官能モノマーおよび／または多官能モノマーを、式（１）で表される化合物と併用してもよい。 《Other monomers》
In the curable composition, a commercially available monofunctional monomer and/or polyfunctional monomer is used in combination with the compound represented by the formula (1) for the purpose of adjusting the mechanical properties of the cured film (tensile strength, abrasion resistance, etc.). You may.
硬化性組成物は、硬化膜の力学物性（引張強度や耐摩耗性など）を調整する目的で、市販の単官能モノマーおよび／または多官能モノマーを、式（１）で表される化合物と併用してもよい。 《Other monomers》
In the curable composition, a commercially available monofunctional monomer and/or polyfunctional monomer is used in combination with the compound represented by the formula (1) for the purpose of adjusting the mechanical properties of the cured film (tensile strength, abrasion resistance, etc.). You may.
（他のモノマーの含有量）
硬化性組成物が他のモノマーを含む場合の硬化性組成物中の他のモノマーの含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０質量％超４０．０質量％未満であることが好ましい。なお、硬化性組成物中の他のモノマーの含有量が硬化性組成物の固形分に対して０．０質量％であるとは、硬化性組成物が他のモノマーを含まないことを意味する。 (Contents of other monomers)
When the curable composition contains another monomer, the content of the other monomer in the curable composition is not particularly limited, but is 0.0% by mass relative to the solid content of the curable composition of the present invention. It is preferably less than 40.0% by mass. The content of the other monomer in the curable composition is 0.0% by mass with respect to the solid content of the curable composition, which means that the curable composition does not contain the other monomer. ..
硬化性組成物が他のモノマーを含む場合の硬化性組成物中の他のモノマーの含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０質量％超４０．０質量％未満であることが好ましい。なお、硬化性組成物中の他のモノマーの含有量が硬化性組成物の固形分に対して０．０質量％であるとは、硬化性組成物が他のモノマーを含まないことを意味する。 (Contents of other monomers)
When the curable composition contains another monomer, the content of the other monomer in the curable composition is not particularly limited, but is 0.0% by mass relative to the solid content of the curable composition of the present invention. It is preferably less than 40.0% by mass. The content of the other monomer in the curable composition is 0.0% by mass with respect to the solid content of the curable composition, which means that the curable composition does not contain the other monomer. ..
《界面活性剤》
硬化性組成物の基材への濡れ性やレベリング性を調整するために、市販の界面活性剤を添加してもよい。 <Surfactant>
A commercially available surfactant may be added in order to adjust the wettability and leveling property of the curable composition to the substrate.
硬化性組成物の基材への濡れ性やレベリング性を調整するために、市販の界面活性剤を添加してもよい。 <Surfactant>
A commercially available surfactant may be added in order to adjust the wettability and leveling property of the curable composition to the substrate.
（界面活性剤の含有量）
硬化性組成物が界面活性剤を含む場合の硬化性組成物中の界面活性剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０質量％超３．０質量％以下であることが好ましい。なお、硬化性組成物中の界面活性剤の含有量が硬化性組成物の固形分の合計質量に対して０．０質量％であるとは、硬化性組成物が界面活性剤を含まないことを意味する。 (Content of surfactant)
The content of the surfactant in the curable composition when the curable composition contains a surfactant is not particularly limited, but is 0.0% by mass based on the solid content of the curable composition of the present invention. It is preferably 3.0% by mass or less. The content of the surfactant in the curable composition is 0.0% by mass based on the total mass of the solid content of the curable composition, and the curable composition does not contain the surfactant. Means
硬化性組成物が界面活性剤を含む場合の硬化性組成物中の界面活性剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０質量％超３．０質量％以下であることが好ましい。なお、硬化性組成物中の界面活性剤の含有量が硬化性組成物の固形分の合計質量に対して０．０質量％であるとは、硬化性組成物が界面活性剤を含まないことを意味する。 (Content of surfactant)
The content of the surfactant in the curable composition when the curable composition contains a surfactant is not particularly limited, but is 0.0% by mass based on the solid content of the curable composition of the present invention. It is preferably 3.0% by mass or less. The content of the surfactant in the curable composition is 0.0% by mass based on the total mass of the solid content of the curable composition, and the curable composition does not contain the surfactant. Means
《重合開始剤》
重合開始剤は、特に限定されないが、例えば、光ラジカル重合開始剤、光カチオン重合開始剤および光アニオン重合開始剤などの光重合開始剤、ならびに熱ラジカル重合開始剤および熱カチオン重合開始剤などの熱重合開始剤が挙げられる。 <Polymerization initiator>
The polymerization initiator is not particularly limited, for example, a photoradical polymerization initiator, a photopolymerization initiator such as a photocationic polymerization initiator and a photoanionic polymerization initiator, and a thermal radical polymerization initiator and a thermal cationic polymerization initiator. A thermal polymerization initiator may be used.
重合開始剤は、特に限定されないが、例えば、光ラジカル重合開始剤、光カチオン重合開始剤および光アニオン重合開始剤などの光重合開始剤、ならびに熱ラジカル重合開始剤および熱カチオン重合開始剤などの熱重合開始剤が挙げられる。 <Polymerization initiator>
The polymerization initiator is not particularly limited, for example, a photoradical polymerization initiator, a photopolymerization initiator such as a photocationic polymerization initiator and a photoanionic polymerization initiator, and a thermal radical polymerization initiator and a thermal cationic polymerization initiator. A thermal polymerization initiator may be used.
（重合開始剤の含有量）
本発明の硬化性組成物が重合開始剤を含む場合の本発明の硬化性組成物中の重合開始剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．１質量％～１０．０質量％であることが好ましく、０．５質量％～８．０質量％であることがより好ましく、１．０質量％～５．０質量％であることがさらに好ましい。 (Content of polymerization initiator)
The content of the polymerization initiator in the curable composition of the present invention when the curable composition of the present invention contains a polymerization initiator is not particularly limited, but with respect to the solid content of the curable composition of the present invention. 0.1 mass% to 10.0 mass% is preferable, 0.5 mass% to 8.0 mass% is more preferable, and 1.0 mass% to 5.0 mass% is preferable. Is more preferable.
本発明の硬化性組成物が重合開始剤を含む場合の本発明の硬化性組成物中の重合開始剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．１質量％～１０．０質量％であることが好ましく、０．５質量％～８．０質量％であることがより好ましく、１．０質量％～５．０質量％であることがさらに好ましい。 (Content of polymerization initiator)
The content of the polymerization initiator in the curable composition of the present invention when the curable composition of the present invention contains a polymerization initiator is not particularly limited, but with respect to the solid content of the curable composition of the present invention. 0.1 mass% to 10.0 mass% is preferable, 0.5 mass% to 8.0 mass% is more preferable, and 1.0 mass% to 5.0 mass% is preferable. Is more preferable.
《重合禁止剤》
硬化性組成物には、式（１）で表される化合物および硬化性組成物の保存安定性を向上させるために、市販の重合禁止剤を添加してもよい。 <Polymerization inhibitor>
A commercially available polymerization inhibitor may be added to the curable composition in order to improve the storage stability of the compound represented by formula (1) and the curable composition.
硬化性組成物には、式（１）で表される化合物および硬化性組成物の保存安定性を向上させるために、市販の重合禁止剤を添加してもよい。 <Polymerization inhibitor>
A commercially available polymerization inhibitor may be added to the curable composition in order to improve the storage stability of the compound represented by formula (1) and the curable composition.
（重合禁止剤の含有量）
硬化性組成物が重合禁止剤を含む場合の硬化性組成物中の重合禁止剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０００５質量％～１．０質量％であることが好ましい。 (Content of polymerization inhibitor)
When the curable composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the curable composition is not particularly limited, 0.0005 mass% relative to the solid content of the curable composition of the present invention. It is preferably from about 1.0% by mass.
硬化性組成物が重合禁止剤を含む場合の硬化性組成物中の重合禁止剤の含有量は、特に限定されないが、本発明の硬化性組成物の固形分に対して、０．０００５質量％～１．０質量％であることが好ましい。 (Content of polymerization inhibitor)
When the curable composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the curable composition is not particularly limited, 0.0005 mass% relative to the solid content of the curable composition of the present invention. It is preferably from about 1.0% by mass.
《溶媒》
溶媒は、特に限定されないが、アルコール、ケトンまたはこれらの混合溶媒が好ましく、炭素数３以下のアルコール、炭素数４以下のケトンまたはこれらの混合溶媒がより好ましい。 "solvent"
The solvent is not particularly limited, but alcohols, ketones, or mixed solvents thereof are preferable, and alcohols having 3 or less carbon atoms, ketones having 4 or less carbon atoms, or mixed solvents thereof are more preferable.
溶媒は、特に限定されないが、アルコール、ケトンまたはこれらの混合溶媒が好ましく、炭素数３以下のアルコール、炭素数４以下のケトンまたはこれらの混合溶媒がより好ましい。 "solvent"
The solvent is not particularly limited, but alcohols, ketones, or mixed solvents thereof are preferable, and alcohols having 3 or less carbon atoms, ketones having 4 or less carbon atoms, or mixed solvents thereof are more preferable.
（溶媒の含有量）
本発明の硬化性組成物が溶媒を含む場合の本発明の硬化性組成物中の溶媒の含有量は、特に限定されないが、本発明の硬化性組成物の全質量に対して、１０．０質量％～９５．０質量％であることが好ましく、３０．０質量％～９０．０質量％であることがより好ましく、５０．０質量％～８０．０質量％であることがさらに好ましい。 (Content of solvent)
The content of the solvent in the curable composition of the present invention when the curable composition of the present invention contains a solvent is not particularly limited, but is 10.0 with respect to the total mass of the curable composition of the present invention. The content is preferably 9% by mass to 95.0% by mass, more preferably 30.0% by mass to 90.0% by mass, and further preferably 50.0% by mass to 80.0% by mass.
本発明の硬化性組成物が溶媒を含む場合の本発明の硬化性組成物中の溶媒の含有量は、特に限定されないが、本発明の硬化性組成物の全質量に対して、１０．０質量％～９５．０質量％であることが好ましく、３０．０質量％～９０．０質量％であることがより好ましく、５０．０質量％～８０．０質量％であることがさらに好ましい。 (Content of solvent)
The content of the solvent in the curable composition of the present invention when the curable composition of the present invention contains a solvent is not particularly limited, but is 10.0 with respect to the total mass of the curable composition of the present invention. The content is preferably 9% by mass to 95.0% by mass, more preferably 30.0% by mass to 90.0% by mass, and further preferably 50.0% by mass to 80.0% by mass.
《その他の添加剤》
本発明の硬化性組成物は、必要に応じて、さらに、その他の添加剤を含んでもよい。
添加剤としては、例えば、粘着付与剤、連鎖移動剤、増感色素、重合阻害抑制剤、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、シランカップリング剤、充填剤、金属粉、および顔料が挙げられる。なお、添加剤は、これらに限定されるものではない。
添加剤の種類、含有量は、適宜選択することができる。 <Other additives>
The curable composition of the present invention may further contain other additives, if necessary.
Examples of the additives include tackifiers, chain transfer agents, sensitizing dyes, polymerization inhibition inhibitors, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, silane coupling agents. Agents, fillers, metal powders and pigments. The additives are not limited to these.
The kind and content of the additive can be appropriately selected.
本発明の硬化性組成物は、必要に応じて、さらに、その他の添加剤を含んでもよい。
添加剤としては、例えば、粘着付与剤、連鎖移動剤、増感色素、重合阻害抑制剤、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、シランカップリング剤、充填剤、金属粉、および顔料が挙げられる。なお、添加剤は、これらに限定されるものではない。
添加剤の種類、含有量は、適宜選択することができる。 <Other additives>
The curable composition of the present invention may further contain other additives, if necessary.
Examples of the additives include tackifiers, chain transfer agents, sensitizing dyes, polymerization inhibition inhibitors, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, silane coupling agents. Agents, fillers, metal powders and pigments. The additives are not limited to these.
The kind and content of the additive can be appropriately selected.
［硬化膜］
本発明の硬化膜は、上述した本発明の硬化性組成物を硬化して得られる硬化膜である。 [Cured film]
The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention described above.
本発明の硬化膜は、上述した本発明の硬化性組成物を硬化して得られる硬化膜である。 [Cured film]
The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention described above.
〈硬化膜の製造方法〉
硬化膜を製造する方法は、特に限定されないが、基材上に本発明の硬化性組成物を配置して、硬化性組成物膜を形成し、硬化性組成物膜を硬化させることが好ましい。
基材上に硬化性組成物膜を形成する方法は、特に限定されないが、例えば、グラビアコーター、コンマコーター、バーコーター、ナイフコーター、ダイコーター、ロールコーター、スピンコーティング、ディッピング、またはペインティングなどによる方法が挙げられる。
硬化性組成物膜を硬化させる方法は、特に限定されないが、光照射または加熱によることが好ましく、光照射によることがより好ましい。特に、基材の耐熱性が低い場合には、光照射により硬化させることが好ましい。光照射は、可視光線、紫外線、電子線、またはガンマ線など、適宜選択すればよい。 <Cured film manufacturing method>
The method for producing a cured film is not particularly limited, but it is preferable to dispose the curable composition of the present invention on a substrate to form a curable composition film and cure the curable composition film.
The method of forming the curable composition film on the substrate is not particularly limited, and for example, gravure coater, comma coater, bar coater, knife coater, die coater, roll coater, spin coating, dipping, painting, or the like. There is a method.
The method for curing the curable composition film is not particularly limited, but irradiation with light or heating is preferable, and irradiation with light is more preferable. In particular, when the heat resistance of the substrate is low, it is preferable to cure it by irradiation with light. The light irradiation may be appropriately selected from visible rays, ultraviolet rays, electron beams, gamma rays and the like.
硬化膜を製造する方法は、特に限定されないが、基材上に本発明の硬化性組成物を配置して、硬化性組成物膜を形成し、硬化性組成物膜を硬化させることが好ましい。
基材上に硬化性組成物膜を形成する方法は、特に限定されないが、例えば、グラビアコーター、コンマコーター、バーコーター、ナイフコーター、ダイコーター、ロールコーター、スピンコーティング、ディッピング、またはペインティングなどによる方法が挙げられる。
硬化性組成物膜を硬化させる方法は、特に限定されないが、光照射または加熱によることが好ましく、光照射によることがより好ましい。特に、基材の耐熱性が低い場合には、光照射により硬化させることが好ましい。光照射は、可視光線、紫外線、電子線、またはガンマ線など、適宜選択すればよい。 <Cured film manufacturing method>
The method for producing a cured film is not particularly limited, but it is preferable to dispose the curable composition of the present invention on a substrate to form a curable composition film and cure the curable composition film.
The method of forming the curable composition film on the substrate is not particularly limited, and for example, gravure coater, comma coater, bar coater, knife coater, die coater, roll coater, spin coating, dipping, painting, or the like. There is a method.
The method for curing the curable composition film is not particularly limited, but irradiation with light or heating is preferable, and irradiation with light is more preferable. In particular, when the heat resistance of the substrate is low, it is preferable to cure it by irradiation with light. The light irradiation may be appropriately selected from visible rays, ultraviolet rays, electron beams, gamma rays and the like.
〈基材〉
基材は、特に限定されないが、例えば、ガラス基材および樹脂基材が挙げられる。
ガラス基材の例は、ソーダ石灰ガラス製基材、ホウケイ酸ガラス製基材、および石英ガラス製基材が挙げられる。ガラス基材の形状は、特に限定されないが、板状であることが好ましい。ガラス基材の表面はコーティングされていてもよいし、プラズマ処理などにより改質されていてもよい。
樹脂基材の例は、ポリエステル系樹脂基材、ポリイミド系樹脂基材、エポキシ系樹脂基材、ポリエーテル系樹脂基材、およびポリスチレン系樹脂基材が挙げられる。樹脂基材の形状は、特に限定されないが、板状またはフィルム状であることが好ましい。樹脂基材の表面はコーティングされていてもよいし、プラズマ処理などにより改質されていてもよい。 <Base material>
The substrate is not particularly limited, but examples thereof include a glass substrate and a resin substrate.
Examples of glass substrates include soda-lime glass substrates, borosilicate glass substrates, and quartz glass substrates. The shape of the glass substrate is not particularly limited, but a plate shape is preferable. The surface of the glass substrate may be coated or may be modified by plasma treatment or the like.
Examples of the resin substrate include a polyester resin substrate, a polyimide resin substrate, an epoxy resin substrate, a polyether resin substrate, and a polystyrene resin substrate. The shape of the resin substrate is not particularly limited, but it is preferably a plate shape or a film shape. The surface of the resin base material may be coated or may be modified by plasma treatment or the like.
基材は、特に限定されないが、例えば、ガラス基材および樹脂基材が挙げられる。
ガラス基材の例は、ソーダ石灰ガラス製基材、ホウケイ酸ガラス製基材、および石英ガラス製基材が挙げられる。ガラス基材の形状は、特に限定されないが、板状であることが好ましい。ガラス基材の表面はコーティングされていてもよいし、プラズマ処理などにより改質されていてもよい。
樹脂基材の例は、ポリエステル系樹脂基材、ポリイミド系樹脂基材、エポキシ系樹脂基材、ポリエーテル系樹脂基材、およびポリスチレン系樹脂基材が挙げられる。樹脂基材の形状は、特に限定されないが、板状またはフィルム状であることが好ましい。樹脂基材の表面はコーティングされていてもよいし、プラズマ処理などにより改質されていてもよい。 <Base material>
The substrate is not particularly limited, but examples thereof include a glass substrate and a resin substrate.
Examples of glass substrates include soda-lime glass substrates, borosilicate glass substrates, and quartz glass substrates. The shape of the glass substrate is not particularly limited, but a plate shape is preferable. The surface of the glass substrate may be coated or may be modified by plasma treatment or the like.
Examples of the resin substrate include a polyester resin substrate, a polyimide resin substrate, an epoxy resin substrate, a polyether resin substrate, and a polystyrene resin substrate. The shape of the resin substrate is not particularly limited, but it is preferably a plate shape or a film shape. The surface of the resin base material may be coated or may be modified by plasma treatment or the like.
〈組成物の用途〉
本発明の組成物は、フォトリソグラフィーなど硬化反応を利用したパターン形成する用途に好適である。例えば、平版印刷版、フレキソ印刷版およびＵＶインクジェット用インクなどの印刷用途、並びに、半導体レジスト材料用途が好ましい。 <Use of composition>
The composition of the present invention is suitable for use in pattern formation using a curing reaction such as photolithography. For example, printing applications such as planographic printing plates, flexographic printing plates and UV inkjet inks, and semiconductor resist material applications are preferable.
本発明の組成物は、フォトリソグラフィーなど硬化反応を利用したパターン形成する用途に好適である。例えば、平版印刷版、フレキソ印刷版およびＵＶインクジェット用インクなどの印刷用途、並びに、半導体レジスト材料用途が好ましい。 <Use of composition>
The composition of the present invention is suitable for use in pattern formation using a curing reaction such as photolithography. For example, printing applications such as planographic printing plates, flexographic printing plates and UV inkjet inks, and semiconductor resist material applications are preferable.
以下では実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
［合成例１］
１．式（１－１）で表される化合物〔化合物（１－１）〕の合成
Ｎ－メチルジエタノールアミン（７ｇ、５８．７ｍｍｏｌ）、テトラヒドロフラン（１００ｍＬ）、およびメタクリル酸２－イソシアナトエチル（１９．６ｇ、１２６ｍｍｏｌ）を混合した。この混合液に、ネオスタンＵ６００（３７７ｍｇ；日東化成社製）をテトラヒドロフラン（５ｍＬ）に希釈した溶液を発熱に注意しながら、滴下し、室温で１２時間撹拌した。この反応の式は以下に示すとおりである。反応溶液を減圧濃縮し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶出液：酢酸エチル～酢酸エチル：メタノール＝９：１）に供することで精製し、化合物（１－１）（２４ｇ、収率９５％）を得た。 [Synthesis example 1]
1. Synthesis of compound represented by formula (1-1) [compound (1-1)] N-methyldiethanolamine (7 g, 58.7 mmol), tetrahydrofuran (100 mL), and 2-isocyanatoethyl methacrylate (19.6 g) , 126 mmol) were mixed. A solution prepared by diluting Neostan U600 (377 mg; manufactured by Nitto Kasei Co., Ltd.) in tetrahydrofuran (5 mL) was added dropwise to this mixed solution while paying attention to heat generation, and the mixture was stirred at room temperature for 12 hours. The equation for this reaction is as follows: The reaction solution was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: ethyl acetate-ethyl acetate:methanol=9:1) to give compound (1-1) (24 g, Yield 95%) was obtained.
１．式（１－１）で表される化合物〔化合物（１－１）〕の合成
Ｎ－メチルジエタノールアミン（７ｇ、５８．７ｍｍｏｌ）、テトラヒドロフラン（１００ｍＬ）、およびメタクリル酸２－イソシアナトエチル（１９．６ｇ、１２６ｍｍｏｌ）を混合した。この混合液に、ネオスタンＵ６００（３７７ｍｇ；日東化成社製）をテトラヒドロフラン（５ｍＬ）に希釈した溶液を発熱に注意しながら、滴下し、室温で１２時間撹拌した。この反応の式は以下に示すとおりである。反応溶液を減圧濃縮し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶出液：酢酸エチル～酢酸エチル：メタノール＝９：１）に供することで精製し、化合物（１－１）（２４ｇ、収率９５％）を得た。 [Synthesis example 1]
1. Synthesis of compound represented by formula (1-1) [compound (1-1)] N-methyldiethanolamine (7 g, 58.7 mmol), tetrahydrofuran (100 mL), and 2-isocyanatoethyl methacrylate (19.6 g) , 126 mmol) were mixed. A solution prepared by diluting Neostan U600 (377 mg; manufactured by Nitto Kasei Co., Ltd.) in tetrahydrofuran (5 mL) was added dropwise to this mixed solution while paying attention to heat generation, and the mixture was stirred at room temperature for 12 hours. The equation for this reaction is as follows: The reaction solution was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: ethyl acetate-ethyl acetate:methanol=9:1) to give compound (1-1) (24 g, Yield 95%) was obtained.
２．化合物（１－２）～化合物（１－４）の合成
化合物（１－１）の合成方法に従って、化合物（１－２）、化合物（１－３）および化合物（１－４）を合成した。 2. Synthesis of Compound (1-2) to Compound (1-4) According to the synthetic method of Compound (1-1), Compound (1-2), Compound (1-3) and Compound (1-4) were synthesized.
化合物（１－１）の合成方法に従って、化合物（１－２）、化合物（１－３）および化合物（１－４）を合成した。 2. Synthesis of Compound (1-2) to Compound (1-4) According to the synthetic method of Compound (1-1), Compound (1-2), Compound (1-3) and Compound (1-4) were synthesized.
３．化合物（Ａ）、化合物（Ｂ）および化合物（Ｃ）の合成
公知の方法により、化合物（Ａ）、化合物（Ｂ）および化合物（Ｃ）を合成した。 3. Synthesis of compound (A), compound (B) and compound (C) Compound (A), compound (B) and compound (C) were synthesized by a known method.
公知の方法により、化合物（Ａ）、化合物（Ｂ）および化合物（Ｃ）を合成した。 3. Synthesis of compound (A), compound (B) and compound (C) Compound (A), compound (B) and compound (C) were synthesized by a known method.
［実施例１～７、比較例１～４］
〈硬化性組成物の調製〉
表１に示す各成分を溶剤に溶解させ、固形分濃度が２０質量％の硬化性組成物（実施例１～７、比較例１～４）を調製した。なお、硬化性組成物において、固形分とは、溶剤以外の全ての成分を意味する。固形分中の化合物（１）の含有量を表１の「化合物（１）の含有量（固形分中）［質量％］」欄に示す。 [Examples 1 to 7, Comparative Examples 1 to 4]
<Preparation of curable composition>
Each component shown in Table 1 was dissolved in a solvent to prepare a curable composition having a solid content concentration of 20% by mass (Examples 1 to 7 and Comparative Examples 1 to 4). In addition, in a curable composition, solid content means all components other than a solvent. The content of the compound (1) in the solid content is shown in the column of "content of compound (1) (in solid content) [mass %]" in Table 1.
〈硬化性組成物の調製〉
表１に示す各成分を溶剤に溶解させ、固形分濃度が２０質量％の硬化性組成物（実施例１～７、比較例１～４）を調製した。なお、硬化性組成物において、固形分とは、溶剤以外の全ての成分を意味する。固形分中の化合物（１）の含有量を表１の「化合物（１）の含有量（固形分中）［質量％］」欄に示す。 [Examples 1 to 7, Comparative Examples 1 to 4]
<Preparation of curable composition>
Each component shown in Table 1 was dissolved in a solvent to prepare a curable composition having a solid content concentration of 20% by mass (Examples 1 to 7 and Comparative Examples 1 to 4). In addition, in a curable composition, solid content means all components other than a solvent. The content of the compound (1) in the solid content is shown in the column of "content of compound (1) (in solid content) [mass %]" in Table 1.
〈硬化膜の作製および経時後の硬化性の評価〉
調製した硬化性組成物を、６０℃で１か月間保管した。なお、保管後の硬化性組成物を経時後の硬化性組成物という場合がある。
経時前および経時後の硬化性組成物を、バーコーターを用いて、乾燥後の厚さが５μｍとなるようにクリアランスを調整して、易接着性ＰＥＴ（ポリエチレンテレフタラート）フィルム（コスモシャインＡ４１００，東洋紡社製；厚み１００μｍ）上に塗布し、乾燥させて硬化性組成物膜を形成した。
次いで、紫外線露光装置（ＨＭＷ－６８０ＧＷ，オーク製作所社製）を用いて、硬化性組成物膜に、紫外線を照射した。この際に、硬化性組成物膜の表面を手で触れたときにべたつきを感じなくなるまでの時間を計測し、経時前と経時後の硬化性組成物膜のべたつきを感じなくなるまでの時間の差を以下の評価基準に従って、経時後の硬化性をＡ～Ｃの３段階で評価した。評価結果を表１に示す。
Ａ：１５秒未満
Ｂ：１５秒以上２０秒未満
Ｃ：２０秒以上３０秒未満
Ｄ：３０秒以上
べたつきを感じなくなるまでの時間の差が短いほど、保管安定性に優れ、経時後の硬化性が優れている。 <Preparation of cured film and evaluation of curability after aging>
The prepared curable composition was stored at 60° C. for 1 month. The curable composition after storage may be referred to as a curable composition after aging.
The curable composition before and after aging was adjusted with a bar coater so that the thickness after drying was 5 μm, and an easily-adhesive PET (polyethylene terephthalate) film (Cosmoshine A4100, The product was applied onto Toyobo Co., Ltd.; thickness 100 μm) and dried to form a curable composition film.
Then, the curable composition film was irradiated with ultraviolet rays using an ultraviolet exposure device (HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.). At this time, the time until the stickiness is no longer felt when the surface of the curable composition film is touched by hand is measured, and the difference between the time until the stickiness of the curable composition film is not felt before and after the lapse of time. According to the following evaluation criteria, the curability after aging was evaluated in three grades A to C. The evaluation results are shown in Table 1.
A: less than 15 seconds B: 15 seconds or more and less than 20 seconds C: 20 seconds or more and less than 30 seconds D: 30 seconds or more The shorter the time difference until stickiness is not felt, the better the storage stability and the curability after aging. Is excellent.
調製した硬化性組成物を、６０℃で１か月間保管した。なお、保管後の硬化性組成物を経時後の硬化性組成物という場合がある。
経時前および経時後の硬化性組成物を、バーコーターを用いて、乾燥後の厚さが５μｍとなるようにクリアランスを調整して、易接着性ＰＥＴ（ポリエチレンテレフタラート）フィルム（コスモシャインＡ４１００，東洋紡社製；厚み１００μｍ）上に塗布し、乾燥させて硬化性組成物膜を形成した。
次いで、紫外線露光装置（ＨＭＷ－６８０ＧＷ，オーク製作所社製）を用いて、硬化性組成物膜に、紫外線を照射した。この際に、硬化性組成物膜の表面を手で触れたときにべたつきを感じなくなるまでの時間を計測し、経時前と経時後の硬化性組成物膜のべたつきを感じなくなるまでの時間の差を以下の評価基準に従って、経時後の硬化性をＡ～Ｃの３段階で評価した。評価結果を表１に示す。
Ａ：１５秒未満
Ｂ：１５秒以上２０秒未満
Ｃ：２０秒以上３０秒未満
Ｄ：３０秒以上
べたつきを感じなくなるまでの時間の差が短いほど、保管安定性に優れ、経時後の硬化性が優れている。 <Preparation of cured film and evaluation of curability after aging>
The prepared curable composition was stored at 60° C. for 1 month. The curable composition after storage may be referred to as a curable composition after aging.
The curable composition before and after aging was adjusted with a bar coater so that the thickness after drying was 5 μm, and an easily-adhesive PET (polyethylene terephthalate) film (Cosmoshine A4100, The product was applied onto Toyobo Co., Ltd.; thickness 100 μm) and dried to form a curable composition film.
Then, the curable composition film was irradiated with ultraviolet rays using an ultraviolet exposure device (HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.). At this time, the time until the stickiness is no longer felt when the surface of the curable composition film is touched by hand is measured, and the difference between the time until the stickiness of the curable composition film is not felt before and after the lapse of time. According to the following evaluation criteria, the curability after aging was evaluated in three grades A to C. The evaluation results are shown in Table 1.
A: less than 15 seconds B: 15 seconds or more and less than 20 seconds C: 20 seconds or more and less than 30 seconds D: 30 seconds or more The shorter the time difference until stickiness is not felt, the better the storage stability and the curability after aging. Is excellent.
表１中の各成分は以下のとおりである。
・モノマー
化合物（１－１） 合成例１で合成したもの
化合物（１－２） 合成例１で合成したもの
化合物（１－３） 合成例１で合成したもの
化合物（１－４） 合成例１で合成したもの
化合物（Ａ） 合成例１で合成したもの
化合物（Ｂ） 合成例１で合成したもの
化合物（Ｃ） 合成例１で合成したもの Each component in Table 1 is as follows.
Monomer Compound (1-1) Synthesized in Synthesis Example 1 Compound (1-2) Synthesized in Synthesis Example 1 Compound (1-3) Synthesized in Synthesis Example 1 Compound (1-4) Synthesis Example 1 Compound (A) Compound synthesized in Synthesis Example 1 Compound (B) Compound synthesized in Synthesis Example 1 Compound (C) Compound synthesized in Synthesis Example 1
・モノマー
化合物（１－１） 合成例１で合成したもの
化合物（１－２） 合成例１で合成したもの
化合物（１－３） 合成例１で合成したもの
化合物（１－４） 合成例１で合成したもの
化合物（Ａ） 合成例１で合成したもの
化合物（Ｂ） 合成例１で合成したもの
化合物（Ｃ） 合成例１で合成したもの Each component in Table 1 is as follows.
Monomer Compound (1-1) Synthesized in Synthesis Example 1 Compound (1-2) Synthesized in Synthesis Example 1 Compound (1-3) Synthesized in Synthesis Example 1 Compound (1-4) Synthesis Example 1 Compound (A) Compound synthesized in Synthesis Example 1 Compound (B) Compound synthesized in Synthesis Example 1 Compound (C) Compound synthesized in Synthesis Example 1
ＴＥＧＤＭＡ （トリエチレングリコールジメタクリレート，下記式で表される化合物；シグマアルドリッチ社製）
TEGDMA (triethylene glycol dimethacrylate, compound represented by the following formula; manufactured by Sigma-Aldrich)
・重合開始剤
Ｏｍｎｉｒａｄ ２９５９（ＩＧＭ Ｒｅｓｉｎｓ社製）
Ｏｍｎｉｒａｄ １１７３（ＩＧＭ Ｒｅｓｉｎｓ社製）
「Ｏｍｉｎｉｒａｄ」は登録商標。 Polymerization initiator Omnirad 2959 (manufactured by IGM Resins)
Omnirad 1173 (made by IGM Resins)
"Ominirad" is a registered trademark.
Ｏｍｎｉｒａｄ ２９５９（ＩＧＭ Ｒｅｓｉｎｓ社製）
Ｏｍｎｉｒａｄ １１７３（ＩＧＭ Ｒｅｓｉｎｓ社製）
「Ｏｍｉｎｉｒａｄ」は登録商標。 Polymerization initiator Omnirad 2959 (manufactured by IGM Resins)
Omnirad 1173 (made by IGM Resins)
"Ominirad" is a registered trademark.
実施例１～７の硬化性組成物は、経時後の硬化性が良好であった。
また、実施例１と実施例３との対比および実施例６と実施例７との対比から、モノマーの種類によらず、含有量が多い方が経時後の硬化性の評価が良好であることが示唆された。
さらに、式（１）中のＲ３の炭素数が少ない化合物（１－１）を使用すると、経時後の硬化性がより良好なものとなることが示唆された。 The curable compositions of Examples 1 to 7 had good curability after aging.
From the comparison between Example 1 and Example 3 and the comparison between Example 6 and Example 7, the higher the content, the better the evaluation of the curability after aging, regardless of the type of the monomer. Was suggested.
Further, it was suggested that the use of the compound (1-1) in which R 3 in the formula (1) has a small number of carbon atoms results in better curability after aging.
また、実施例１と実施例３との対比および実施例６と実施例７との対比から、モノマーの種類によらず、含有量が多い方が経時後の硬化性の評価が良好であることが示唆された。
さらに、式（１）中のＲ３の炭素数が少ない化合物（１－１）を使用すると、経時後の硬化性がより良好なものとなることが示唆された。 The curable compositions of Examples 1 to 7 had good curability after aging.
From the comparison between Example 1 and Example 3 and the comparison between Example 6 and Example 7, the higher the content, the better the evaluation of the curability after aging, regardless of the type of the monomer. Was suggested.
Further, it was suggested that the use of the compound (1-1) in which R 3 in the formula (1) has a small number of carbon atoms results in better curability after aging.
Claims (4)
- 式（１）で表される化合物を固形分中に６０．０質量％超含む硬化性組成物。
式（１）中、Ｒ１およびＲ２は、それぞれ独立に、水素原子またはアルキル基を表す。Ｒ１が複数であるとき、複数のＲ１は互いに同じであってもよいし異なっていてもよい。Ｒ２が複数であるとき、複数のＲ２は互いに同じであってもよいし異なっていてもよい。Ｒ３は、水素原子または１価の置換基を表す。Ｒ１ＡおよびＲ１Ｂは、それぞれ独立に、酸素原子または－ＮＲ１０１－を表す。Ｒ１０１は水素原子またはアルキル基を表す。Ｒ１Ａが複数であるとき、複数のＲ１Ａは互いに同じであってもよいし異なっていてもよい。Ｒ２Ａが複数であるとき、複数のＲ２Ａは互いに同じであってもよいし異なっていてもよい。Ｌ１は、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ２０１－を含んでいてもよく、環構造を含まないａ＋１価の脂肪族炭化水素基、または、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ２０１－を含んでいてもよく、芳香族環構造を含むａ＋１価の炭化水素基を表す。Ｌ３は、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、環構造を含まないｃ＋１価の脂肪族炭化水素基、または、ウレタン結合を含み、－Ｏ－もしくは－ＮＲ３０１－を含んでいてもよく、芳香族環構造を含むｃ＋１価の炭化水素基を表す。Ｒ２０１は水素原子またはアルキル基を表す。Ｒ３０１は水素原子またはアルキル基を表す。ａおよびｃは、それぞれ独立に、１～３の整数を表す。 Curable composition which contains the compound represented by Formula (1) in solid content more than 60.0 mass %.
In formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group. When R 1 is plural, R 1 may be different or may be the same as each other. When R 2 is plural, plural R 2 may be the same as or different from each other. R 3 represents a hydrogen atom or a monovalent substituent. R 1A and R 1B each independently represent an oxygen atom or —NR 101 —. R 101 represents a hydrogen atom or an alkyl group. When R 1A is plural, R 1A may be different may be the same as each other. When R 2A is a plurality, the plurality of R 2A may be different may be the same as each other. L 1 contains a urethane bond and may contain —O— or —NR 201 —, an a+1-valent aliphatic hydrocarbon group containing no ring structure, or a urethane bond, —O— or — NR 201 -may be included and represents an a+1-valent hydrocarbon group containing an aromatic ring structure. L 3 contains a urethane bond and may contain —O— or —NR 301 —, and contains a c+1-valent aliphatic hydrocarbon group containing no ring structure, or contains a urethane bond, —O— or — NR 301 -may be included and represents a c+1-valent hydrocarbon group containing an aromatic ring structure. R 201 represents a hydrogen atom or an alkyl group. R 301 represents a hydrogen atom or an alkyl group. a and c each independently represent an integer of 1 to 3. - 前記Ｒ３が炭素数４以下のアルキル基である、請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein R 3 is an alkyl group having 4 or less carbon atoms.
- 前記式（１）で表される化合物を固形分中に６５．０質量％超含む、請求項１または２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the solid content of the compound represented by the formula (1) is more than 65.0% by mass.
- 請求項１～３のいずれか１項に記載の硬化性組成物を硬化して得られる硬化膜。 A cured film obtained by curing the curable composition according to any one of claims 1 to 3.
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| US4867680A (en) * | 1987-03-31 | 1989-09-19 | Dentsply Research & Development Corp. | Pre-loaded dental impression package and method of making |
| JP2013506718A (en) * | 2009-08-28 | 2013-02-28 | スリーエム イノベイティブ プロパティズ カンパニー | Compositions and articles comprising a polymerizable ionic liquid mixture and curing method |
| JP2018178115A (en) * | 2017-04-13 | 2018-11-15 | 東洋インキＳｃホールディングス株式会社 | Multi-branched urethane compound-containing polymerizable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867680A (en) * | 1987-03-31 | 1989-09-19 | Dentsply Research & Development Corp. | Pre-loaded dental impression package and method of making |
| JP2013506718A (en) * | 2009-08-28 | 2013-02-28 | スリーエム イノベイティブ プロパティズ カンパニー | Compositions and articles comprising a polymerizable ionic liquid mixture and curing method |
| JP2018178115A (en) * | 2017-04-13 | 2018-11-15 | 東洋インキＳｃホールディングス株式会社 | Multi-branched urethane compound-containing polymerizable composition |
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