JPH07300458A - Polymerizable imide compound and photocurable composition - Google Patents

Abstract

PURPOSE:To obtain the subject new compound excellent in solubility to organic solvents, and capable of improving the photocurability and heat resistance of heat-resistant photosensitive resins, thus useful for the coating materials in the electronic industry, etc., and as a raw material for heat-resistant photoresists, etc. CONSTITUTION:This compound is expressed by the formula [R<1> is a 2-20C C=C bond-contg. organic group such as vinyl, vinylidene or (meth)acrylic group], e.g. a compound where R<1> is methacryloyloxyethylene. This illustrated compound is obtained by reaction between 2-methacryloyloxyethyl isocyanate and 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride in DMF in the presence of tri-n-butylamine and phenothiazine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymerizable imide compound and a photocurable composition containing the same.

[0002]

2. Description of the Related Art In recent years, heat-resistant photosensitive resins have been used as coating materials, heat-resistant photoresists, mainly in the fields of electrical and electronic industries.
Widely used as an adhesive and potting agent.

It is desired that the heat-resistant photosensitive resin of this kind has excellent photocurability and heat resistance after photocuring as its original characteristics.

However, there are few conventionally known heat-resistant photosensitive resins which satisfy these requirements. In general, most of those having excellent photocurability are inferior in heat resistance after photocuring.

In order to avoid such drawbacks, a benzophenone type polymerizable imide compound is disclosed in JP-A-3-271272.
It is proposed in Japanese Patent Publication No. However, since this type of polymerizable imide compound has a problem of solubility, there is a limit to the organic solvent used for dissolving and diluting. Further, when it is dissolved in the photosensitive resin, there is a problem that it is necessary to use a limited organic solvent.

[0006]

The present invention has been made to solve the above-mentioned problems, and it is possible to form a heat-resistant photosensitive resin cured product which satisfies the above-mentioned required characteristics, and further various It is an object of the present invention to provide a new and useful polymerizable imide compound having excellent solubility in an organic solvent. Another object of the present invention is to provide a photocurable composition capable of forming a heat-resistant photosensitive resin cured product as described above and capable of being liquefied without using an organic solvent.

[0007]

The polymerizable imide compound of the present invention has the general formula (I)

[0008]

[Chemical 2]

(In the formula, R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 30 carbon atoms).

R ¹ in the above general formula is a polymerizable carbon-
It is not particularly limited as long as it is an organic group having a carbon double bond and having 2 to 30 carbon atoms, but usually has a vinyl group, a vinylidene group, an acryl group or a methacryl group (both are abbreviated as (meth) acryl group) Is preferred. As a specific example

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

(In the formula, m is an integer of 0 to 8 and n is 2 to 12)
, R ² represents —H or —CH _3, and the like.

The polymerizable imide compound of the present invention can be used for various polymerization reactions by utilizing its double bond, but it is particularly preferably used for photopolymerization reaction and is used together with a photopolymerizable resin which is usually used. When used as, a remarkable effect is exhibited.

Therefore, the present invention secondly provides a photocurable composition comprising a polymerizable imide compound represented by the general formula (I), a photosensitive resin and a photoinitiator as essential components.

In the present invention, the photosensitive resin means an organic material which is polymerized or cured by irradiation with light in the presence of a photoinitiator, and the molecular state may be any of a monomer, an oligomer and a polymer. Used.
Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) as a photosensitive monomer.
Acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethyl (Meth) acrylate monomers such as glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethyl (meth) acrylamide, N-methyl (meth) acrylamide , (Meth) acryloylmorpholine and other (meth)
In addition to acrylamide monomers, vinyl monomers and the like can be exemplified. Further, known polymers such as photosensitive polyamic acid, photosensitive polyimide and photosensitive polyamideimide can be exemplified. The above-mentioned monomers and polymers may be used in the form of oligomers. Moreover, you may use together 2 or more types.

As the photoinitiator, for example, acetophenone, diethoxyacetophenone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzyl, methyl benzoyl formate, thioxanthone, diethyl thioxanthone,
2,2-dimethoxy-2-phenylacetophenone, 1
-Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like can be mentioned. These can be used alone 2
You may use together 1 or more types.

The polymerizable imide compound (A) represented by the general formula (I) and the photosensitive resin (B) have a ratio (A) / (B) (weight ratio) of 5/95 to 80/20. It is preferably used.

The photoinitiator is a component (A) and a component (B) 1
It is preferably used in the range of 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 00 parts by weight. If this amount is too small, the sensitivity tends to decrease, and if it is too large, the stability tends to decrease.

The photocurable composition of the present invention may be dissolved in an appropriate amount of an organic solvent before use. The organic solvent is not particularly limited in type as long as it can dissolve the polymerizable imide compound represented by the general formula (I) of the present invention and the photoinitiator to be used and does not impair workability such as coating. In particular,
For example, sulfolane, N, N-dimethylacetamide,
Examples thereof include N, N-dimethylformamide, N-methyl-2-pyrrolidone, ethyl acetate, acetone, methanol, chloroform and tetrahydrofuran.

In preparing the photocurable composition of the present invention, there is no particular limitation on the mixing order, mixing method, etc. of the imide compound represented by the general formula (I), the photosensitive resin and the photoinitiator. It can be performed according to the technique.

The photocurable composition of the present invention can be used in applications such as adhesion, coating, potting, etc. after being dissolved in an appropriate amount of an organic solvent as needed depending on the method of use.

When the photocurable composition of the present invention is irradiated with an actinic ray, polymerization occurs in the irradiated part to form a heat-resistant photosensitive resin cured product. Ultraviolet rays are usually used as the actinic rays, but in some cases, electron beams,
Ionizing radiation such as radiation can also be used.

The photocurable composition of the present invention may use an organic solvent, but as long as the component system other than the polymerizable imide compound is liquid, it is easily stable without using a solvent. A heat-resistant photosensitive resin cured product having higher heat resistance can be formed by forming a liquid and having excellent adhesiveness to a substrate, and performing heat treatment after photocuring.

[0028]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 2-methacryloyloxyethyl isocyanate was added to a 30 ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride 1.752 g (4 mmol), tri-n-butylamine 0.037 g (0.2 mmol), phenothiazine 7 m.
g, 10 ml of N, N-dimethylformamide was charged,
Stir with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid.

Infrared absorption spectrum of the solid obtained (IR-700 infrared spectrophotometer manufactured by JASCO Corporation, K
Analytical results by Rs method) shown in FIG. ^1, 1 H-NMR
The analysis results by (JEOL Ltd. FX-200 type nuclear magnetic resonance spectrometer) are shown in FIG. No. 1 in FIG. 1 (2952 cm ⁻¹ ) of —CH ₂ —, —C
Absorption based on H ₃ , No. 3, 4 (1779, 1719)
cm ⁻¹ ) based on imidocarbonyl absorption, No. 5
Absorption based on C = C at (1637 cm ⁻¹ ) was observed. Further, as shown in FIG. 2, all the proton peaks are assigned, and their integrated intensity ratios are also Aromat.
_{ic H, H = 6, -C} H 2 -N-, H = 4,
_{-O-C H 2 -, H} = 4, -C H 3, H = 6,
= C H ₂ , H = 4, which was in agreement with the theoretical value. Furthermore, when elemental analysis was performed, the measured value was N: C: H = 4.1.
2: 55.76: 3.50 and theoretical value N: C: H =
It almost coincided with 4.20: 55.86: 3.62. From the above, the general formula (I) (R ¹ : —CH ₂ —CH ₂ —
It was confirmed that a polymerizable imide compound represented by O—CO—C (CH ₃ ) ═CH ₂ ) was obtained.

Example 2 Obtained general formula (I) (R ¹ : --CH ₂ --CH ₂ --O--
In order to confirm the solubility of the polymerizable imide compound represented by CO—C (CH ₃ ) ═CH ₂ ) in the organic solvent, the compound represented by the general formula (I)
_{^{(R 1: -CH 2 -CH 2}} -O-CO-C (CH 3) =
30 mg of a polymerizable imide compound represented by CH ₂ ) was added to 1 ml of an organic solvent, and the mixture was stirred with a magnetic stirrer for 5 minutes at room temperature. Table 1 shows the organic solvent used and the results of the organic solvent solubility test.

Example 3 The obtained general formula (I) (R ¹ : --CH ₂ --CH ₂ --O--
In order to confirm the solubility of the polymerizable imide compound represented by CO—C (CH ₃ ) ═CH _{2 in} the photosensitive resin, the compound represented by the general formula (I) (R ¹ : —CH ₂ —CH ₂ —O—CO— C (CH
₃ ) = CH ₂ ) polymerizable imide compound 10 mg
Was added to 0.5 ml of a photosensitive resin, and the mixture was stirred with a magnetic stirrer for 5 minutes at room temperature. The photosensitive resin used and the result of the photosensitive resin solubility test are shown in Table 2.

Example 4 The obtained general formula (I) (R ¹ : --CH ₂ --CH ₂ --O--
CO-C (CH ₃ ) = CH ₂ ) 0.2 g of a polymerizable imide compound, 0.2 g of 2-hydroxyethyl methacrylate as a photosensitive resin, and 1-phenyl-2-hydroxy-2- as a photoinitiator. Methylpropan-1-one (0.02 g) and chloroform (2 g) were stirred and mixed, and then coated on a glass plate and vacuum dried to obtain a resin coating film. afterwards,
It was irradiated with ultraviolet rays of 2700 mJ / cm ² to obtain a photocurable resin coating film.

The thermal decomposition temperature (10% weight loss temperature) was measured by TG measurement of the photocured resin coating film, and the results are shown in Table 3.
Shown in.

Example 5 The obtained general formula (I) (R ¹ : --CH ₂ --CH ₂ --O--
_{CO-C (CH 3) =} CH 2) polymerizable imide compound represented by 0.2g, isobornyl methacrylate 0.2g as a photosensitive resin, as a photoinitiator 1-phenyl-2-
Hydroxy-2-methylpropan-1-one 0.02
g and 2 g of chloroform were mixed by stirring, then applied on a glass plate and vacuum dried to obtain a resin coating film. Then 2700
Ultraviolet rays of mJ / cm ² were irradiated to obtain a photocurable resin coating film.

The thermal decomposition temperature (10% weight loss temperature) was measured by TG measurement of the photocured resin coating film, and the results are shown in Table 3.
Shown in.

Comparative Example 1 2-methacryloyloxyethyl isocyanate was added to a 30 ml capacity two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 1.289 g (4 m
mol), 0.037 g of tri-n-butylamine (0.
2 mmol), phenothiazine 7 mg, and N, N-dimethylformamide 10 ml are charged, and the mixture is stirred with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform was carried out, followed by recrystallization with acetone, filtration and vacuum drying to obtain a white solid.

The solid obtained was analyzed by elemental analysis, infrared absorption spectrum analysis and ¹ H-NMR analysis to obtain the compound of the general formula (I
It was confirmed that the polymerizable imide compound represented by I) was obtained.

[0039]

[Chemical 8]

Comparative Example 2 To confirm the solubility of the obtained polymerizable imide compound represented by the general formula (II) in an organic solvent, 30 mg of the polymerizable imide compound represented by the general formula (II) was added to 1 ml of an organic solvent. And stirred with a magnetic stirrer for 5 minutes at room temperature. Table 1 shows the organic solvent used and the results of the organic solvent solubility test.

Comparative Example 3 In order to confirm the solubility of the obtained polymerizable imide compound represented by the general formula (II) in a photosensitive resin, 10 mg of the polymerizable imide compound represented by the general formula (II) was used as a photosensitive compound. Resin 0.
It was added to 5 ml and stirred with a magnetic stirrer for 5 minutes at room temperature. The photosensitive resin used and the result of the photosensitive resin solubility test are shown in Table 2.

Comparative Example 4 0.4 g of 2-hydroxyethyl methacrylate as a photosensitive resin, 0.02 g of 1-phenyl-2-hydroxy-2-methylpropan-1-one as a photoinitiator, and 2 g of chloroform were stirred and mixed. It was applied on a glass plate and vacuum dried to obtain a resin coating film. After that, 2700 mJ / cm
^It was irradiated with ultraviolet rays of ² to obtain a photocurable resin coating film.

The thermal decomposition temperature (10% weight loss temperature) was measured by TG measurement of the photocured resin coating film, and the results are shown in Table 3.
Shown in.

Comparative Example 5 Isobornyl methacrylate 0.4 as a photosensitive resin
g, 1-phenyl-2-hydroxy-2 as a photoinitiator
-Methylpropan-1-one (0.02 g) and chloroform (2 g) were stirred and mixed, and then coated on a glass plate and vacuum dried to obtain a resin coating film. Then, it was irradiated with 2700 mJ / cm ² of ultraviolet rays to obtain a photocurable resin coating film.

The thermal decomposition temperature (10% weight loss temperature) was measured by TG measurement of the photocured resin coating film, and the results are shown in Table 3.
Shown in.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the polymerizable imide compound obtained in Example 1.

2 is a nuclear magnetic resonance spectrum of the polymerizable imide compound obtained in Example 1. FIG.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/027 514

Claims (2)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 30 carbon atoms). 2. A photocurable composition comprising the polymerizable imide compound according to claim 1, a photosensitive resin and a photoinitiator.