JP2002322214A - Reactive polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound enabling the curing reaction and pattern formation in the form of a thin film, etc., by heat, light or the presence of a polymerization initiator and provide a monomer for the polymer compound. SOLUTION: The reactive polymer compound having polymerizable unsaturated bond group is produced by the homopolymerization of a monomer having two or more kinds of polymerizable unsaturated bond groups in the molecular structure or the copolymerization of the monomer and a monomer copolymerizable with the former monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monomer having two or more kinds of polymerizable unsaturated bond groups in a molecular structure and a reactive polymer compound obtained by polymerizing the monomer.

[0002]

2. Description of the Related Art In recent years, semiconductor manufacturing technology has made rapid progress. The miniaturization and quantification of electronic devices are being pushed strongly. Along with this, small communication devices typified by mobile phones have become much easier to handle as compared with conventional ones, and have been widely spread because they are mass-produced at low cost.
Such advances in technology are based on miniaturization and high integration of semiconductor devices. In other words, this is the result of advancing higher integration of the circuit formed on the semiconductor chip itself, miniaturization of the circuit by reducing the package size, thinning of a package sealing material for protecting the chip, and the like. Along with this, the technology to use a protective film on the circuit on the chip surface to secure the reliability of the semiconductor and the technology to multi-stage the circuit via an interlayer insulating film have been vigorously developed. Materials that can withstand use are also strongly desired.

On the other hand, new technologies have been introduced in semiconductor packages for encapsulating semiconductor chips, and technologies such as multichip modules, ball grid arrays, and chip scale packages enable high-density mounting. It is becoming. These semiconductor packages use a substrate made of a material such as plastic or ceramics to connect the electrodes of the semiconductor chip to the printed wiring board. The circuit on the substrate is introduced into a miniaturized semiconductor, and can be made higher in density than a conventional printed wiring board. Therefore, it is necessary to protect the fine wiring. In addition, new technologies such as a build-up method have been developed for printed circuit boards, and higher densities of wiring have been measured.

[0004] These protective resins or interlayer insulating resins are required to have heat resistance at the time of mounting and hole workability. conventionally,
A polyimide resin has been mainly used, but an epoxy resin has been used especially when low-temperature workability is required.
Furthermore, a photosensitive resin is advantageous for performing pattern processing of holes and the like corresponding to a circuit wiring having a high density. A typical example is a photosensitive polyimide (JP-B-55-30-30).
207, JP-A-54-145794, etc.). The photosensitive polyimide forms a crosslinked structure by photoradical polymerization of methacrylate introduced into a carboxyl group of polyamic acid, and performs pattern processing. At the time of conversion to polyimide later, methacrylate needs to be desorbed, and stronger heating than usual is required. In addition, the remaining methacrylate degrades the material properties when remaining, so that it is necessary to decompose and volatilize the released methacrylate at a high temperature in order to exhibit the original performance. Therefore, such photosensitive polyimide requires high-temperature treatment. As another method, there has been proposed a resin in which an acrylate structure is introduced into a side chain of a preliminarily closed polyimide to realize low-temperature processability (Japanese Patent Application Laid-Open No. 59-10803).
No. 1) cannot satisfy properties such as heat resistance. Epoxy resins were not sufficiently heat resistant or flexible to follow the deformation of the substrate.

[0005] As described above, while the semiconductor manufacturing technology has made remarkable progress, the technology of optical communication or optical information processing has also advanced rapidly. Even in fields that have traditionally relied on electronic technology, optical technology has penetrated from long distances to short distances, from ultra-high speeds to ultra-high densities. Is spreading. For optical components such as optical fibers and optical waveguides that support such optical transmission technology, optical materials having various required characteristics such as transparency, heat resistance, optical isotropy, and workability are required. Regarding transparency, although many amorphous polymer materials are transparent in the visible range, the harmonics of vibration absorption of carbon-hydrogen bonds or oxygen-hydrogen bonds are transparent in the near infrared region, which is the communication wavelength range. It is a factor that lowers. As an attempt to improve this, the conversion of a hydrocarbon skeleton into a fluorocarbon, the introduction of a siloxane skeleton, and the like have been studied. Regarding heat resistance, a rigid skeleton polyimide, a strong siloxane skeleton, or a crosslinked structure has been studied. With respect to optical isotropy, it is desirable that components having optical anisotropy such as aromatic rings are not oriented,
Since the rigid skeleton for improving the heat resistance promotes the orientation of the molecules, the heat resistance and the optical isotropy usually tend to be contradictory. With regard to processability, for example, in the case of optical waveguides, it mainly refers to the formability of the core / cladding structure, but when spin-coating a high molecular weight polymer material from a solution, intermixing is likely to occur, resulting in poor waveguide processability. There are many problems. On the other hand, in the type in which a low-molecular-weight oligomer is formed into a film and then cross-linked by light or heat, the formed reactive polymer compound after cross-linking is insolubilized in a solvent, thereby preventing intermixing. As a result, there is a tendency that many of them have excellent workability.

As described above, although there are problems that have been individually solved as conventional techniques, excellent optical materials satisfying the characteristics required as optical components have not been developed at present. It is.

As a compound having two polymerizable unsaturated bonding groups in a molecule, a compound in which two hydroxyls of a diol are terminated by an acryloyl group, a methacryloyl group, an α-trifluoromethylacryloyl group or the like is known. For example, it is described in Japanese Unexamined Patent Application Publication No. 7-191286 that polymerization is used for a soft contact lens. However, there is no description about controlling the reactivity of two polymerizable unsaturated bond groups in a molecule to obtain a reactive polymer compound, and using the compound.

A compound having 2 to 6 acryloyloxy groups or methacryloyloxy groups and having a fluorine-containing double bond-containing group is disclosed in JP-A-8-319257.
However, there is no description about an α-trifluoroalkylacryloyloxy group.

[0009]

An object of the present invention is to provide a polymer compound capable of undergoing a curing reaction or pattern formation by heat, light or the presence of a polymerization initiator after being formed into a thin film or the like, and a monomer as a raw material thereof. To provide.

[0010]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that a monomer having a part capable of radical polymerization and a part capable of ionic polymerization in its molecular structure. A reactive polymer compound obtained by polymerization by either radical polymerization or ionic polymerization can be dissolved in a general-purpose solvent, so that a thin film can be formed by coating or the like, and the formed thin film is subjected to heat, light, or polymerization. Since it can be cured by the presence of the initiator, it can be a highly transparent and tough film, and it is also possible to form a pattern, and it has been found that it has remarkable utility for optical applications, The present invention has been completed.

The present invention relates to a monomer having two or more types of polymerizable unsaturated bonding groups in a molecular structure, and a polymerizable unsaturated bonding group obtained by polymerizing the monomer alone or together with a copolymerizable monomer. Is a reactive polymer compound. The reactive polymer compound of the present invention is very useful as an electronic material such as a semiconductor element or a circuit wiring board, an optical material such as an optical waveguide, an optical integrated circuit, an optical fiber, or an antireflection film, and further a material for a printing plate. It is.

Hereinafter, the present invention will be described in detail.

The monomer having two or more polymerizable unsaturated bond groups in the molecular structure according to the present invention is a monomer having at least a radical polymerizable group and an ionic polymerizable group. The ionic polymerizable group may be either an anionic polymerizable group or a cationic polymerizable group. These polymerizable unsaturated groups may have two or more types selected from the groups described below. The radical polymerizable group capable of radical polymerization includes the following general formula (6) or (7)
And an organic group containing at least one carbon-carbon unsaturated bond represented by the following formula:

[0014]

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In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent a hydrogen atom or an organic group. R ⁹ and R ¹⁰ , or R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ , or R ⁹ and R ¹⁰ and R ¹¹ may be connected to form a cyclic structure.

The radical polymerizable group is preferably an acryloyl group or a methacryloyl group or a group containing them.

The partial structure of the anionic polymerizable group capable of anionic polymerization is represented by the general formula (6), wherein at least one of R ⁹ , R ¹⁰ and R ¹¹ is an electron-withdrawing substituent. A certain structure is preferable, and a substituent conjugated with a carbon-carbon unsaturated bond is also preferable. The electron-withdrawing substituents referred to herein include fluorine, chlorine,
Halogen atoms such as bromine and iodine, halogenated alkyl groups, R—C (＝ O) — (R represents an organic group) group, cyano group, aromatic groups such as benzene ring, halogen-substituted aromatic groups, halogenated alkyl-substituted aromatic group, a cyano group-substituted aromatic group, or _{R-CH = CH 2, -} (R represents an organic group) and a group is preferable. Further, a substituent represented by the general formula (7) in which R ¹² is a hydrogen atom or an organic group is also preferable.
Further, as the partial structure capable of anionic polymerization, a partial structure including a ring structure having an electron-withdrawing atom or a substituent is preferably employed. A monomer containing an α-trifluoromethylacryloyl group as a partial structure as the anionic polymerizable group is particularly preferably used.

The partial structure of the cationically polymerizable group capable of cationic polymerization is represented by the following general formula (6), wherein at least one of R ⁹ , R ¹⁰ and R ¹¹ is an electron-donating substituent. Certain structures are preferred. The electron donating substituent referred to herein includes a Group 16 element such as oxygen, sulfur and selenium adjacent to a carbon-carbon unsaturated bond of the general formula (6), or a Group 15 element such as nitrogen and phosphorus, Or carbon,
Substituents containing elements belonging to Group 14 such as silicon, germanium, tin, and lead are mentioned. An example of a partial structure capable of cationic polymerization is represented by the general formula (6), wherein R ⁹ ,
At least one of R ¹⁰ and R ¹¹ is an alkyl group, R—O—
(R represents an organic group) group, R—C (＝ O) —O— group (R
Represents an organic group), an alkylated group 14 element substituent such as an alkylsilyl group, an alkylgermyl group, an alkyltin group, an alkyllead group, or a substituent in which a part of the alkyl group is substituted by an alkoxy group is preferable. Adopted. Also, represented by the general formula (6), wherein at least one of R ⁹ , R ¹⁰ , and R ¹¹ includes an aromatic group such as a benzene ring, an alkyl-substituted aromatic group, a carbazole group, a norbornyl group, an adamantyl group, and the like. Substituents are preferably employed. Further, a general formula (7) in which R ¹⁰ is a hydrogen atom or an organic group
The substituent represented by is also preferably adopted. R ⁹ ,
As R ¹⁰ and R ¹¹ , a group containing a ring structure having an electron-donating atom or a substituent is also preferably employed.

As the monomer having two or more types of polymerizable unsaturated bond groups in the molecular structure of the present invention, the two or more types of polymerizable unsaturated bond groups in the molecular structure include at least a radical polymerizable group and an ionic polymerizable group. Preferred are monomers that are groups.

The monomer used in the present invention has a radical polymerizable group and an ionic polymerizable group in its molecular structure, and the portion connecting these groups must be one that does not significantly inhibit the properties of the reactive polymer compound. There is no particular limitation. For example, a divalent organic group, a divalent atom, a divalent inorganic group, and the like can be given. The divalent organic group is preferably a hydrocarbon group having about 1 to 40 carbon atoms and containing about 1 to 20 oxygen. Among them, -O- (C
H ₂₎ group (m represented by _m -O- represents an integer of 1~20), -. O-R 4 - 2 divalent organic group is preferably represented by, specifically, R ⁴ As an oxyalkylene group which may have a branch having about 1 to 20 carbon atoms,
6 or more of the number of repetitions of opening of the alkylene oxide of 6
A polyoxyalkylene group of 0 or the like is preferable, and more specifically, ethylene oxide, propylene oxide or tetrahydrofuran has 1 to 20 repeating cycles.
The polyoxyalkylene group is preferably employed because of easiness of synthesis of the monomer.

Examples of the monomer having two or more types of polymerizable unsaturated bond groups in the molecular structure include those represented by the general formula (1):

[0022]

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(Wherein, R ¹ represents a radical polymerizable group and R ⁴ represents an organic group), α-trifluoromethyl acrylate represented by the general formula (2):

[0024]

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(Wherein, R ² represents a hydrogen atom or a methyl group; R ³ represents an ionic polymerizable group; and R ⁴ represents an organic group). Here, R ¹ and R ³ are the above-mentioned radical polymerizable groups or ionic polymerizable groups, respectively.

The monomer having two or more types of polymerizable unsaturated bond groups in the molecular structure includes a compound represented by the following general formula (3):

[0027]

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(Wherein, R ⁴ represents an organic group, and R ⁵ represents a hydrogen atom or a methyl group). R ⁴ is preferably an oxyalkylene group or a polyoxyalkylene group described above. And the like, and the general formula (4)

[0029]

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(Wherein, R ⁶ represents a hydrogen atom or a methyl group; m represents an integer of 1 to 20);

[0031]

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(Wherein, n represents an integer of 1 to 20; R ⁶ ,
R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, and either R ⁷ or R ⁸ represents a hydrogen atom. Is more preferable.

Such compounds are shown below without limitation.

[0034]

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The α-trifluoromethylacrylic ester represented by the general formula (1) is composed of α-trifluoromethylacrylic halide (chloride, bromide, fluoride) or α-trifluoromethylacrylic anhydride and R ¹ alcohols comprising a radically polymerizable group and the coupling group represented by -R ⁴ -OH obtained by esterification. The method of esterification may be a known method performed for acrylic acid or methacrylic acid.

The acrylic acid ester or methacrylic acid ester represented by the general formula (2) is obtained by mixing (meth) acrylic acid halide (chloride, bromide, fluoride) or (meth) acrylic anhydride with R ³ -R ⁴ -OH By esterifying an alcohol comprising an ionic polymerizable group represented by and a bonding group. The method of esterification may be a known method performed for acrylic acid or methacrylic acid.

The reactive polymer compound of the present invention can be obtained by polymerization by either radical polymerization or ionic polymerization. The polymerization reaction at this time may be either homopolymerization or copolymerization with other monomers. You may. When synthesized by radical polymerization, a monomer having radical polymerizability is used as a copolymerization component. Examples thereof include ethylene, propylene, α-olefins such as butene-1, methyl acrylate, ethyl acrylate, n- Propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, cyclohexyl acrylate or iso Acrylic esters such as bornyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, - butyl methacrylate, n- pentyl methacrylate, n
-Hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate or methacrylic acid esters such as isobornyl methacrylate, cycloolefins such as cyclobutane or cyclopentane , Methyl vinyl ether, ethyl vinyl ether,
n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl Vinyl ethers such as vinyl ether, phenylethyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; allyls such as methyl allyl ether, ethyl allyl ether, n-propyl allyl ether, isopropyl allyl ether, n-butyl allyl ether, and isobutyl allyl ether Ethers, allyls Ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, aliphatic carboxylic acid vinyl VeoVa 9 (C _9, VeoVa 10 (C ₁₀ branched aliphatic carboxylic acid vinyl), branched aliphatic carboxylic acids vinyl VeoVa 11 (C _11), vinyl stearate, vinyl-2,2-dimethyl propanoate, vinyl-2,2-dimethyl butanoate,
Vinyl-2,2-dimethylpentanoate, vinyl-2,2-
Dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylpentanoate, vinyl-3-chloro-2,2-dimethylpropanoate, vinyl cyclohexanecarboxylate , Vinyl esters such as vinyl methylcyclohexanecarboxylate, vinyl benzoate or vinyl pt-butyl benzoate; styrene-based monomers such as styrene, α-methylstyrene or vinyltoluene; dienes such as butadiene and isoprene; and trienes. Etc. are preferably used. At this time, it is also preferable to copolymerize a fluorine-containing monomer for the purpose of increasing the fluorine content of the reactive polymer compound. Examples of the fluorine-containing monomer include 2,
2,2-trifluoroethyl acrylate, 2,2
3,3-tetrafluoropropyl acrylate, 2,
2,3,3,3-pentafluoropropyl acrylate, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl acrylate, 2,2,2-trifluoro-
1-trifluoromethylethyl acrylate, 2,2
3,4,4,4-hexafluorobutyl acrylate,
2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3-tetrafluoro-1-methylpropyl acrylate, 2,2,3,3,4,4,4
5,5-octafluoropentyl acrylate, 2,
2,3,3,4,4,5,5,5-nonafluoropentyl acrylate, 2,2,3,3-tetrafluoro-
1,1-dimethylpropyl acrylate, 2,2,3
4,4,4-hexafluoro-t-hexyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7
-Dodecafluoroheptyl acrylate, 2,2,3
3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl acrylate, 2,2,3,3,4
4,5,5-octafluoro-1,1-dimethylpentyl acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl acrylate, 3,3,4 , 4,5,5,6,6,7,
7,8,8-dodecafluorooctyl acrylate,
3,3,4,4,5,5,6,6,7,7,8,8,8
-Tridecafluorooctyl acrylate, 2-hydroxy-4,4,5,5,6,7,7,7-octafluoro-6-trifluoromethylheptyl acrylate,
2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9-hexadecafluorononyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10-hexadecafluorodecyl acrylate, 3,3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate, 2-hydroxy-4,4,
Fluorinated acrylic esters such as 5,5,6,6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2 , 2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,2
2 ′, 2 ′, 2′-hexafluoroisopropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3
4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,5-nonafluoropentyl methacrylate, 2,2,3,3-tetrafluoro-1,1 -Dimethylpropyl methacrylate,
2,2,3,4,4,4-hexafluoro-1,1-dimethylbutyl methacrylate, 2,2,3,3,4
4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 2,2,3,3,4,4,5,5
6,6,7,7,7-tridecafluoroheptyl methacrylate, 2,3,4,5,5,5-hexafluoro-
2,4-bis (trifluoromethyl) pentyl methacrylate, 2,2,3,3,4,4,5,5,6,6
7,7,8,8-tetradecafluorooctyl methacrylate, 2,2,3,3,4,4,5,5,6,6
7,7,8,8,8-pentadecafluorooctyl methacrylate, 2-hydroxy-4,4,5,5,6
7,7,7-octafluoro-6-trifluoromethylheptyl methacrylate, 2,2,3,3,4,4
5,5,6,6,7,7,8,8,9,9,10,10
-Octadecafluorodecyl methacrylate, 2,2
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-nonadecafluorodecyl methacrylate, 2-hydroxy-4,4,5,5,6,
Fluorinated methacrylates such as 6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl methacrylate, fluorinated styrene-based monomers, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, Fluoroolefins such as vinyl fluoride and hexafluoropropylene, chlorofluoroolefins such as chlorotrifluoroethylene, fluorine-containing vinyl ethers, fluorine-containing vinyl esters, fluorine-containing allyl ethers, fluorine-containing allyl esters, and fluorine-containing dienes And fluorine-containing trienes. For example, when used as an optical material, it is possible to improve the transparency in a specific wavelength range and to lower the refractive index. Further, the physical properties can be adjusted by changing the type and amount of the monomer to be copolymerized.

When the reactive polymer compound of the present invention is synthesized by ionic polymerization, an ionic polymerizable monomer can be used as a copolymer component. When the ionic polymerization is an anionic polymerization, it is represented by the general formula (8) as a comonomer, wherein R ¹³ , R ¹⁴ ,
A monomer having a structure in which at least one of R ¹⁵ and R ¹⁶ is an electron-withdrawing substituent is preferable, and a substituent conjugated to a carbon-carbon unsaturated bond is also preferable.

[0039]

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The electron-withdrawing substituents referred to herein include a halogen atom such as fluorine, chlorine, bromine and iodine, a halogenated alkyl group, or R—C (＝ O) —.
(R represents an organic group), a cyano group, an aromatic group such as a benzene ring, a halogen-substituted aromatic group, a halogenated alkyl-substituted aromatic group, a cyano-substituted aromatic group, or RC
An H = CH ₂ — (R represents an organic group) group or the like is preferable.
Further, a monomer having a structure represented by the general formula (9) in which R ¹⁷ and R ¹⁸ are a hydrogen atom or an organic group is also preferable. Further, monomers containing a ring structure having an electron-withdrawing atom or a substituent are also preferably employed. Further, a monomer containing an α-trifluoromethylacryloyl group is more preferably used. Specific examples thereof include methyl ester, ethyl ester, and n-trifluoromethyl acrylate.
Propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, pentyl ester, cyclohexyl ester, hydroxymethyl ester,
-Hydroxyethyl ester, 3-hydroxypropyl ester, 4-hydroxybutyl ester, 5-hydroxypentyl ester, 6-hydroxyhexyl ester and the like, and 3,3,3-trifluoroethyl-α-trifluoromethyl Acrylate, hexafluoroisopropyl-α-trifluoromethyl acrylate and the like can be exemplified. When a monomer having a fluorinated group in the ester moiety is used as an optical material, it is possible to improve the transparency in a specific wavelength range or to lower the refractive index. Further, the physical properties can be adjusted by changing the type and amount of the monomer to be copolymerized.

The partial structure of the cationically polymerizable group capable of cationic polymerization is represented by the general formula (6), wherein at least one of R ⁹ , R ¹⁰ and R ¹¹ is an electron donating substituent. Certain structures are preferred. The electron donating substituent referred to herein includes a Group 16 element such as oxygen, sulfur and selenium adjacent to a carbon-carbon unsaturated bond of the general formula (6), or a Group 15 element such as nitrogen and phosphorus, Or carbon,
Substituents containing elements belonging to Group 14 such as silicon, germanium, tin, and lead are mentioned. An example of a partial structure capable of cationic polymerization is represented by the general formula (6), wherein R ⁹ ,
At least one of R ¹⁰ and R ¹¹ is an alkyl group, R—O—
(R represents an organic group) group, R—C (＝ O) —O— group (R
Represents an organic group), an alkylated group 14 element substituent such as an alkylsilyl group, an alkylgermyl group, an alkyltin group, an alkyllead group, or a substituent in which a part of the alkyl group is substituted by an alkoxy group is preferable. Adopted. Also, represented by the general formula (6), wherein at least one of R ⁹ , R ¹⁰ , and R ¹¹ includes an aromatic group such as a benzene ring, an alkyl-substituted aromatic group, a carbazole group, a norbornyl group, an adamantyl group, and the like. Substituents are preferably employed. Further, a general formula (7) in which R ¹² is a hydrogen atom or an organic group
The substituent represented by is also preferably adopted. R ⁹ ,
As R ¹⁰ and R ¹¹ , a group containing a ring structure having an electron-donating atom or a substituent is also preferably employed.

When the reactive polymer compound of the present invention is synthesized by cationic polymerization, a cationically polymerizable monomer can be used as a copolymer component. An example thereof is represented by the general formula (8), wherein R ¹³ ,
A structure in which at least one of R ¹⁴ , R ¹⁵ and R ¹⁶ is an electron donating substituent is preferred. The electron-donating substituents referred to herein include Group 16 elements such as oxygen, sulfur and selenium adjacent to the carbon-carbon unsaturated bond of the general formula (8),
Alternatively, a monomer having a structure containing a Group 15 element such as nitrogen or phosphorus, or a Group 14 element such as carbon, silicon, germanium, tin, or lead may be used. Specifically, general formula (8)
Wherein at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is
Alkylation of alkyl group, alkylsilyl group, alkylgermyl group, alkyltin group, alkyllead group, etc.
A group 4 element substituent or a substituent in which a part of the alkyl group is substituted with an alkoxy group is preferably employed. Also represented by the general formula (8), wherein R ¹³ , R ¹⁴ , R ¹⁵ , R
^At least one of ¹⁶ is an aromatic group such as a benzene ring, an alkyl-substituted aromatic group, a carbazole group, a norbornyl group,
A monomer having a structure containing an adamantyl group or the like is preferably employed. Further, a substituent represented by the general formula (9) in which R ¹⁷ and R ¹⁸ are a hydrogen atom or an organic group is also preferably employed. In the formula, a monomer having a ring structure having an electron donating atom or a substituent as R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ is also preferably employed.

The reactive polymer compound of the present invention can have a plurality of types of radically polymerizable groups or a plurality of ionic polymerizable groups, for example, for the purpose of enhancing the curing reactivity after molding. .

As the reactive polymer compound of the present invention, a monomer having two or more types of polymerizable unsaturated bond groups in the molecular structure represented by the general formula (1):

[0045]

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(Wherein R ¹ represents a radical polymerizable group and R ⁴ represents an organic group), α-trifluoromethyl acrylate represented by the general formula (2):

[0047]

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Wherein R ² represents a hydrogen atom or a methyl group; R ³ represents an ionic polymerizable group; and R ⁴ represents an organic group. It is preferably a reactive polymer compound obtained by polymerization with a monomer copolymerizable with the monomer.

The reactive polymer compound of the present invention is represented by the general formula (10)

[0050]

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(In the formula, R ¹ represents a radical polymerizable group and R ⁴ represents an organic group.) A reactive polymer compound containing a repeating unit represented by the following formula is preferred.

Further, the reactive polymer compound of the present invention includes a compound represented by the following general formula (11):

[0053]

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(In the formula, R ² represents a hydrogen atom or a methyl group; R ³ represents an ionic polymerizable group; and R ⁴ represents an organic group.) A reactive polymer compound containing a repeating unit represented by the formula: .

Hereinafter, the method for producing the reactive polymer compound of the present invention will be described in detail.

The reactive polymer compound of the present invention is synthesized by radical polymerization or ionic polymerization. The polymerization may be carried out by any of batch, semi-continuous or continuous operations according to known forms such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Is changed as appropriate. The container used for the polymerization reaction is not particularly limited.

In the method for producing the reactive polymer compound of the present invention by radical polymerization, the polymerization reaction temperature is usually preferably from 20 to 200 ° C., particularly preferably from 50 to 140 ° C. Further, a polymerization solvent may be used. The polymerization solvent is not particularly limited, but preferably does not significantly inhibit polymerization, is selected in consideration of the solubility of the monomer to be used and the solubility of the reactive polymer compound to be generated, the polymerization method and It can be appropriately changed depending on the form of polymerization. Examples of the polymerization solvent used in the radical polymerization,
Ketone solvents such as acetone and methyl isobutyl ketone; aromatic solvents such as toluene, xylene and benzene; cyclic hydrocarbon solvents such as cyclopentane and cyclohexane; alcohols such as isopropyl alcohol, t-butanol and ethylene glycol monomethyl ether Examples of the solvent include ester solvents such as ethyl acetate, methyl acetate, n-butyl acetate, isobutyl acetate, and t-butyl acetate. It is also possible to add a dispersant or an emulsifier to water for polymerization. Further, a molecular weight modifier such as mercaptan may be used in combination.

Examples of the polymerization initiator include, but are not particularly limited to, azo compounds, peroxide compounds, and redox compounds. In particular, azobisisobutyronitrile, t-butyl Peroxypivalate,
Benzoyl peroxide and the like are preferred.

As an emulsifier for performing emulsion polymerization,
An anionic emulsifier or a nonionic emulsifier can be used. Examples of the anionic emulsifier include an alkylbenzene sulfonate, an alkyl sulfate, a polyoxyethylene alkylphenol sulfate, a styrene sulfonate, and derivatives thereof. Examples of these salts include salts derived from alkali metal hydroxides, and salts derived from ammonia or a volatile base such as triethylamine. Also,
Examples of the nonionic emulsifier include polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, fluoroalkyl carboxylate, fluoroalkyl sulfate and the like. . The radical polymerization initiator is not particularly limited as long as it is used for general emulsion polymerization, and among these, a water-soluble initiator is particularly preferably applicable.

Examples of the water-soluble initiator include peroxides such as hydrogen peroxide, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, disuccinic peroxide, and diglutaric peroxide. Azo initiators such as organic peroxides, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, azobisisobutylamidine hydrochloride, azobisisobutyronitrile, azobiscyanovaleric acid, and the like A redox initiator comprising a combination of an initiator and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium bisulfite, sodium metabisulfite, sodium bithiosulfate, sodium formaldehyde sulfoxylate, reducing sugars,
Further, an initiator system in which a small amount of iron, ferrous salt, silver sulfate, copper sulfate and the like coexist as a metal in these combinations can be used. The method for adding these radical initiators may be batch addition at the start of polymerization or divisional addition during the reaction.

As a method for producing the reactive polymer compound of the present invention by ionic polymerization, the polymerization reaction temperature is usually preferably from -200 to 100 ° C, particularly preferably from -100 to 50 ° C.
C is preferred. Further, a polymerization solvent may be used. The polymerization solvent is not particularly limited, but preferably does not significantly inhibit polymerization, is selected in consideration of the solubility of the monomer to be used and the solubility of the reactive polymer compound to be generated, the polymerization method and It can be appropriately changed depending on the form of polymerization.

As examples of the polymerization solvent used in the anionic polymerization, an aprotic solvent is preferable, and a polar solvent is preferably used. For example, tetrahydrofuran, diethyl ether, ethers such as 1,4-dioxane,
An aprotic polar solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide is preferably used.
In the case of a monomer having high anionic polymerization reactivity, water or alcohols may be used as an initiator, but this is not a limitation. A method in which a non-polar solvent and a phase transfer catalyst such as a crown ether are used in combination is also preferable. As the initiator for the anionic polymerization, those generally used can be used and are not particularly limited, but commercially available organic lithium compounds such as n-butyllithium and t-butyllithium, or diphenylhexyl It is possible to use a highly stable lithium compound such as lithium. Further, metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium-t-butoxide, and potassium-t-butoxide are preferably used. Also, pyridine, picoline, lutidine,
Nitrogen-containing heterocyclic compounds such as piperidine and amines such as triethylamine, tributylamine and triethanolamine are also preferably used.

Examples of the polymerization solvent used in the cationic polymerization
Pentane, hexane, heptane, octane, etc.
Aliphatic hydrocarbon solvents, benzene, toluene, xy
Aromatic hydrocarbon solvents such as ren, dichloromethane,
Halogenated hydrocarbon solvents such as chloroform, nitrite
And the like. As an initiator for cationic polymerization
In general, commonly used ones can be used.
Not specified, but called electrophilic compound or Lewis acid
The compound can be an initiator. There are several types
But protonic acids such as hydrogen chloride and metal oxides
Bronsted acid, halogen, metal halide, organic gold
Genus compounds, stable cations and the like correspond to this. concrete
Proton acids include phosphoric acid, sulfuric acid, hydrogen chloride,
Hydrogen fluoride, hydrogen fluoride, hydrogen iodide, perchloric acid, hypochlorite
Acid, nitric acid, p-toluenesulfonic acid, sulfonic acid, vinegar
Acid, trifluoroacetic acid, trifluoromethanesulfonic acid
And so on. Of metal oxides and other solid acids
Examples include chromium oxide, molybdenum oxide, silica-a
Solid acids such as lumina, or their complexes,
Bond the ion exchange resin or protonic acid to the appropriate compound.
Or adsorbed substances. Examples of halogen
As iodine, bromine, chlorine, fluorine, IBr, ICl, Br
Cl, and the like. Also, as an example of a metal halide,
Aluminum chloride, aluminum bromide, titanium tetrachloride
Tan, titanium tetrabromide, tin chloride, tin bromide, anti chloride
Mon, iron chloride, rhenium chloride, zinc chloride, cadmium chloride
, Niobium fluoride, tantalum fluoride, magnesium chloride
And boron trifluoride. Organometallic compounds
Examples of triethylaluminum, diethyl chloride
Aluminum, ethyldichloroaluminum, etc.
Killed aluminum or alkyl halide aluminum
System, alkyl zinc compound, ethyl magnesium bromide
And methylmagnesium bromide
Drug, (C₂H₅)₂TiCl ₂AlCl₂Ziegler-based initiators such as
Can be given. Stable cations include
Phenylcarbonium ion or tropylium ion
Stable salts of carbonium ions, such as
Ph₃CSbCl₆Or Ph₃CSnCl₅Can give
Wear. As other examples, tetracyanoethylene,
Electrophilicity of vinylidene cyanide, maleic anhydride, etc.
Strong compounds can also be used as a type of initiator
You.

As a method for removing the organic solvent or water as a medium from the solution or dispersion of the reactive polymer compound of the present invention thus obtained, any known method can be used. For example, a method of filtering after reprecipitation or a method of heating or not heating under normal pressure or reduced pressure or the like can be employed.

The number average molecular weight of the reactive polymer compound of the present invention is usually 1,000 to 1,000,000, and preferably 10,000 to 500,000. When the molecular weight is smaller than 1,000, the strength as a high molecular compound becomes low, and the molecular weight becomes 1,000,000.
If it exceeds 00, the solubility of the solvent becomes small. However, depending on the purpose of use, it may contain a cross-linked structure of a part of the molecular structure. For example, it may be formed into a gel or a form dispersed in water or an organic solvent and then subjected to a reaction such as curing to complete the formation. It is also possible to stabilize.

The reactive polymer compound of the present invention can be subjected to various curing methods, and is not particularly limited.
When the reactive polymer compound is obtained by ionic polymerization and all or a part of the radical reactive group remains, it is possible to perform a crosslinking reaction by adding a radical polymerization initiator. is there. At this time, a crosslinking reaction may be performed by a radical species generated by heating by adding a peroxide or the like, or a crosslinking reaction may be performed by adding a photopolymerization initiator such as benzophenone and irradiating light. As examples of the radical polymerization initiator, the same ones as those exemplified when synthesizing the reactive polymer compound by radical polymerization can be used. Examples of the photopolymerization initiator include benzophenone, Micheler's ketone, xanthone, thioxanthone, 2-chlorothioxanthone, anthraquinone,
Aromatic ketones such as ethylanthraquinone, acetophenone, trichloroacetophenone, 2-hydroxy-
2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, benzoin isobutyl ether,
Acetophenones such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone; diketones such as benzyl and methylbenzoylformate; 1-phenyl-1,2-propanedione-2
Acyl oxime esters such as-(O-benzoyl) oxime, thiols, disulfides, organic peroxides such as benzoyl peroxide, azo compounds, halides such as carbon tetrabromide, quinoxaline, 1,3- Dioxolan and the like. Alternatively, the crosslinking reaction can also be performed by partially subjecting the reactive polymer compound itself to radical cleavage with light or heat without adding a radical polymerization initiator. It is also preferable to use a sensitizer in order to efficiently perform a photoreaction.

Furthermore, it is also possible to add another radical-reactive monomer or oligomer, another reactive polymer compound, etc. during the curing (cross-linking) reaction and copolymerize. Here, as the copolymerizable monomer or the like, the radical polymerizable monomers listed as monomers copolymerizable when synthesizing the present reactive polymer compound can be used. In addition, any other compound having radical polymerizability can be appropriately used as needed.

The composition when copolymerized with the reactive polymer compound is not particularly limited, and can be arbitrarily set as long as the properties of the reactive polymer compound are not significantly impaired.

The reactive polymer compound formed into a film or the like can be partially irradiated with light using a photomask in the presence or absence of a catalyst to form a partially cured pattern. In order to develop the pattern after curing, a method such as washing with a solvent capable of dissolving only the uncured portion is adopted. By such a method, a protective film is formed on a part of the semiconductor wiring,
It is possible to form an optical waveguide or to form a cladding layer or a coating layer of an optical fiber.

On the other hand, when the reactive polymer compound obtained by radical polymerization has all or a part of the ionic polymerization reactive group remaining, it can be crosslinked by adding an ionic polymerization initiator. It is. In both anionic polymerization and cationic polymerization, the same initiators as those exemplified as the method for synthesizing the reactive polymer compound can be used.

Also, a cationic photopolymerization initiator can be used,
Onium salts such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts and the like can be used.
Using the ionic polymerization reactive group, patterning can be performed in the same manner as in the photoradical polymerization described above. At the time of the ionic crosslinking reaction, it is also possible to add another ion-reactive monomer or oligomer, another reactive polymer compound, or the like to copolymerize. Here, as the copolymerizable monomer, the same monomer as the ion-polymerizable monomer described in synthesizing the present reactive polymer compound by ionic polymerization can be used. In addition, any other compound having ionic polymerizability can be appropriately used as needed. The composition for copolymerization is not particularly limited, and can be arbitrarily set as long as the properties of the reactive polymer compound are not significantly impaired.

[0072]

EXAMPLES Hereinafter, the present invention will be described in more detail by reference examples and examples, but embodiments of the present invention are not limited thereto.

<Example 1> Synthesis of monomer represented by the following formula (hereinafter sometimes abbreviated as αCF3-HEMA)

[0074]

Embedded image

A glass reactor equipped with a stirrer, a dropping funnel and a thermometer was charged with hydroxyethyl methacrylate (HEM).
A) 18.4 g, 100 m of dehydrated tetrahydrofuran
15.2 g of 1,2,6-lutidine was charged and the inside of the reactor was replaced with nitrogen. The bottom of the reactor was cooled with an ice bath. Next, α-trifluoromethylacrylic acid chloride was diluted with 53 ml of dehydrated tetrahydrofuran, charged into a dropping funnel, and slowly dropped. After the dropping was completed in about 45 minutes, the ice bath was removed from the reactor, the temperature was gradually raised to room temperature, and stirring was continued for 2 hours. After completion of the reaction, the reaction solution was poured into 500 ml of ice water and stirred. After washing with water three times, dehydration was performed with anhydrous sodium sulfate, and αCF3-HEMA was obtained by distillation under reduced pressure. Boiling point 85-88 ° C / 3mmHg.
Yield 19.2 g (69% yield). ¹ H-N of αCF3-HEMA (deuterated chloroform solvent, internal standard tetramethylsilane)
MR is shown in FIG.

Example 2 Synthesis of Radical-Reactive Polymer Compound by Anionic Polymerization of αCF3-HEMA (Anionic Homopolymerization of αCF3-HEMA) 9.6 g of αCF3-HEMA was placed in a glass reactor equipped with a stirrer.
0.05 g of pyridine was charged, and stirring was started at room temperature.
The reaction solution gradually increased in viscosity and became difficult to stir, and was left as it was. Sixteen hours after the start of the reaction, tetrahydrofuran was added to dissolve the polymer, and then n-hexane 5
The solution was added to 00 ml and reprecipitated. The resulting white precipitate was filtered out and dried at 40 ° C. under vacuum to obtain a white solid polymer. Yield 6.0 g (yield 63
%). A part of the obtained resin is dissolved in tetrahydrofuran and subjected to gel permeation chromatography (GP).
According to C), the molecular weight using polystyrene as a standard substance was measured. As a result, the molecular weight and its distribution were as follows: number average molecular weight (Mn) = 10,000, weight average molecular weight (M
w) = 19,000, molecular weight dispersion (Mw / Mn) = 1.
Nine. The solubility in the solvent was soluble in acetone, methyl isobutyl ketone (MIBK), and tetrahydrofuran, but was insoluble in n-hexane.

Example 3 Thermal Radical Crosslinking of Radical Reactive Polymer Compound 2.0 g of the reactive polymer compound obtained in Example 2 was dissolved in methyl isobutyl ketone to prepare a 10 wt% solution. To this solution was added t-butyl peroxypivalate 0.0
1 g was added, mixed, and cast on a glass plate with an applicator. After air drying at room temperature for 5 minutes, it was heated in an oven at 80 ° C. for 1 hour. The film formed on the glass plate is transparent, acetone, methyl isobutyl ketone (MIB
K), insoluble in tetrahydrofuran and n-hexane.

Example 4 Synthesis of Radical-Reactive Polymer Compound by Anionic Polymerization of αCF3-HEMA (Anionic Copolymerization of αCF3-HEMA and αCF3-3F) A glass reactor equipped with a stirrer was placed in a glass reactor. -Trifluoroethyl-α-trifluoromethyl acrylate (αCF
7.0 g, αCF3-HEMA 2.0 g, and pyridine 0.025 g were charged, and stirring was started at room temperature. The reaction solution gradually increased in viscosity and became difficult to stir, and was left as it was. Sixteen hours after the start of the reaction, tetrahydrofuran was added to dissolve the polymer, and then n-hexane 500
and reprecipitated. The resulting white precipitate was filtered out and dried at 40 ° C. under vacuum to obtain a white solid polymer. Yield: 6.8 g (76% yield).
A part of the obtained resin was dissolved in tetrahydrofuran, and the molecular weight was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. As a result, the molecular weight and its distribution were as follows: number average molecular weight (Mn) = 45,000, weight average molecular weight (Mw) = 6
4,000, molecular weight dispersion (Mw / Mn) = 1.4. The composition ratio of the structural units of the copolymer obtained from the measurement of nuclear magnetic resonance (NMR) is αCF3-3F / αCF
3-HEMA = about 85/15. Solubility in solvents is acetone, methyl isobutyl ketone (MIBK),
It was soluble in tetrahydrofuran and insoluble in n-hexane.

Example 5 Photoradical Crosslinking of Radical-Reactive Polymer Compound 2.0 g of the reactive polymer compound obtained in Example 4, hexafluoroisopropyl acrylate (HFIPA)
A solution was prepared by mixing 2.0 g and 36.0 g of methyl isobutyl ketone. 0.1 g of benzophenone
Was added and dissolved, and cast on a glass plate with an applicator. Place a mask pattern on top of this and use a high pressure mercury lamp to
Light was applied for 0 minutes. After the light irradiation, the entire glass plate was placed in an acetone solvent, and the unexposed portions were dissolved and removed. The film formed on the exposed portion was transparent and was insoluble in acetone, methyl isobutyl ketone (MIBK), tetrahydrofuran, and n-hexane.

[0080]

According to the present invention, when a monomer having two or more types of polymerizable unsaturated bond groups is used in the molecular structure of the present invention, a highly reactive polymer having completely different structures, physical properties and crosslinking properties can be obtained by selecting a polymerization method. Since a molecular compound can be obtained, and the reactive polymer compound can be cross-linked using light, heat, a radical initiator or an ionic polymerization initiator, it has an effect that it can be used for forming a pattern of a thin film.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a product obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08G 65/332 C08G 65/332 4M109 H01L 23/29 H01L 23/30 D 23/31 (72) Inventor Tsutsumi Kentaro 2805 Imafukunakadai, Kawagoe-shi, Saitama F-term in the Chemical Research Laboratories of Central Glass Co., Ltd. WA01 4J027 AA02 AB03 AB32.

Claims (14)

[Claims] 1. A polymerizable polymer having a polymerizable unsaturated bonding group obtained by polymerizing a monomer having two or more kinds of polymerizable unsaturated bonding groups alone or together with a monomer copolymerizable with the monomer. High molecular compounds. 2. The reactive polymer compound according to claim 1, wherein the two or more polymerizable unsaturated bond groups are at least a radical polymerizable group and an ionic polymerizable group. 3. The polymerizable unsaturated bond group according to claim 1, wherein the at least two types of polymerizable unsaturated bonding groups are at least a radical polymerizable group and an ionic polymerizable group, and the reactive polymer compound is any one of a radical polymerizable group and an ionic polymerizable group. The reactive polymer compound according to claim 1, having a reactive unsaturated group. 4. A monomer having two or more polymerizable unsaturated bond groups in a molecular structure represented by the general formula (1): (Wherein, R ¹ represents a radical polymerizable group and R ⁴ represents an organic group), or α-trifluoromethyl acrylate represented by the general formula (2): (Wherein, R ² represents a hydrogen atom or a methyl group; R ³ represents an ionic polymerizable group; and R ⁴ represents an organic group). Reactive polymer compound. 5. A compound of the general formula (10) (In the formula, R ¹ represents a radical polymerizable group, and R ⁴ represents an organic group.) A reactive polymer compound containing a repeating unit represented by the following formula: 6. A compound of the general formula (11) (Wherein, R ² represents a hydrogen atom or a methyl group; R ³ represents an ionic polymerizable group; and R ⁴ represents an organic group). 7. The reactive polymer compound according to claim 1, which is cured by heat or light. 8. A reactive polymer compound composition comprising the reactive polymer compound according to claim 1 and at least an ionic polymerization initiator. 9. A monomer having at least a radical polymerizable group and an ionic polymerizable group in a molecular structure. 10. An α-trifluoromethyl acrylate represented by the following general formula (1). Embedded image (In the formula, R ¹ represents a radical polymerizable group, and R ⁴ represents an organic group.) 11. An acrylate or methacrylate represented by the following general formula (2). Embedded image (In the formula, R ² represents a hydrogen atom or a methyl group. R ³ represents an ionic polymerizable group, and R ⁴ represents an organic group.) 12. A compound represented by the following general formula (3). Embedded image (In the formula, R ⁴ represents an organic group. R ⁵ represents a hydrogen atom or a methyl group.) 13. A compound represented by the following general formula (4). Embedded image (In the formula, R ⁶ represents a hydrogen atom or a methyl group.
Represents an integer of 20. ) 14. A compound represented by the following general formula (5). Embedded image (In the formula, n represents an integer of 1 to 20. R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom or a methyl group, and any of R ⁷ and R ⁸ represents a hydrogen atom.)