JPS58167568A - Photopolymerizable imide monomer - Google Patents

Abstract

NEW MATERIAL:A photopolymerizable imide monomer shown by the formula II (R is bifunctional organic group). USE:Useful as a raw material for forming a cured material of a heat-resitant resin. Having a cinnamoyl group sharply inductive by light rays in the molecule, having improved photosetting properties, improved stability as a photosetting composition in a solution state, not being gelatinized in a short period even by allowing it to stand at room temperature. Providing a material to be bonded with improved adhesiveness, forming a cured material of a heat-resistant resin having improved characteristics such as heat resistance, electrical insulating properties, water vapor resistance, chemical resistance, etc. after photosetting. PROCESS:An imide-amine shown by the formula II is reacted with a cinnamic acid shown by the formula III (X is hydroxyl group, alkoxy, preferably 1-5C alkoxy or halogen) or its derviative in an organic solvent such as N,N-dimethylformamide, etc. or in the absence of a solvent, to give a compound shown by the formulaI. The amount of the compound shown by the formula III is 1.7-2.2 times the molar quantity of the compound shown by the formula II.

Description

[Detailed description of the invention] The present invention relates to photopolymerizable imide monomers.

In recent years, heat-resistant photosensitive resins have been widely used in the electrical and electronic industries as covering materials, insulating materials, solder resists, adhesives, heat-resistant photoresists, and the like.

Such heat-resistant photosensitive resins are required not only to have excellent photocurability and heat resistance after photocuring, but also to have good adhesion to adherends. Furthermore, it is required to have excellent properties such as insulation properties, moisture resistance, and chemical resistance. On the other hand, from the viewpoint of non-pollution and resource saving, it is possible to form a film in a solvent-free system or with a small amount of solvent, and to gel over time before use. It is required that no hindrance be caused.

However, there are few conventionally known heat-resistant photosensitive resins that satisfy all of these required properties, and those with excellent photocurability tend to have poor storage stability, and also have poor adhesion. Many of them lack adhesion to the body.

The present invention was made to solve the above problems, and it not only has excellent storage stability, photosensitivity, and adhesion to adherends, but also has poor heat resistance after photocuring. The object of the present invention is to provide a new and useful photopolymerizable imide monomer that forms a heat-resistant cured resin that satisfies all of the above-mentioned properties. Another object of the present invention is to provide a method for producing the above-mentioned photopolymerizable imide monomer and a photocurable composition that forms the above-mentioned heat-resistant resin cured product.

The photopolymerizable imide monomer according to the present invention has the general formula (however,
R represents a divalent organic group. ).

In the above general formula, R preferably represents a divalent aliphatic, aromatic or alicyclic hydrocarbon group, and preferable specific examples include Alkirev Ji having 2-20 carbon atoms, jtl having 6-
20 represents a phenylene group, an alkylphenylene group, and a divalent organic group of the following general formula %. ), a cyclohexylene group, an alkylcyclohexylene group, and the like.

According to the present invention, the photopolymerizable imide monomer as described above is an imidoamine represented by the general formula (wherein R is the same as above) and a general formula (where X is a hydroxyl group, an alkoxy group, preferably represents an alkoxy group having 1 to 5 carbon atoms or a halogen.

As the derivative of cinnamic acid, specifically, cinnamic acid methyl ester, cinnamic acid chloride, etc. are used, but cinnamic acid chloride, which reacts rapidly under mild reaction conditions, is preferably used.

The cinnamic acid or its derivative is reacted in an amount of 1.7 to 2.2 times the molar amount, preferably 2 times the molar amount, relative to the -F imide alcohol.

As the organic solvent, one that can dissolve both the reactant and the reaction product is preferably used, and specifically, N, N-
Polar aprotic organic solvents such as dimethylformamide, N,N-dimedylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoramide, and dimethyl sulfoxide are preferably used. Cresol, methylene chloride, etc. are also preferably used alone or as a mixed solvent with the above solvents. When using cinnamic acid chloride as the cinnamic acid derivative, it is advantageous to use amines such as trimethylamine, diethylamine, triethylamine, tripropylamine, pyridine, and cyclohexylamine as the dehydrochlorination agent. In this case, the reaction usually proceeds smoothly at a temperature of 5 to 70°C. The time required for the reaction is usually 1 to 20 hours. After the reaction, the product imide compound can be obtained as a precipitate by adding a non-solvent for the product, typically water, to the reaction solution.

The imidoamine used in the above reaction is already known, and usually, 1.3 to 2.5 times the mole, preferably 2 times the mole amount of imidoamine to 1.2.3.4-butanetetracarboxylic acid or its acid anhydride. It is obtained by reacting a diamine represented by the formula % formula % (where R is the same as above) under heating in an organic solvent or in the absence of a solvent (Japanese Patent Publication No. 1973-
No. 47837). When a solvent is used, the above-mentioned polar aprotic organic solvents, cresol, and the like are preferably used. Examples of the diamine include m-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenylethane, 4.4'-diaminodiphenylpropane, 4.4'
-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,4'-dimethoxybenzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-
Diaminodiphenylsulfone, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene/, 4,4'-diaminobiphenyl, m-xylylenediamine, p-xylylenediamine, bis(4-aminophenoxy)benzene, −
aminocyclohexyl)methane, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4゜4'-dimethyl hebutadiamine, 3-methoxy hebutamethylene diamine, 2,1
1-diaminododecane, 1.1-diaminocyclohexane, 2.2'-diaminodiethyl ether, 2.2'-
Diaminodiethylthioether, 3,3'-diaminodipropoxyethane, 2,6-diamitubiridine, guanamine, 2,5-diamino-1,3,4-oxadiazole, 2-(3'-aminophenyl)-5- Aminobenzoxazole, bis(4-aminophenyl)diethylsilane, etc. are used.

The photopolymerizable imide monomer according to the present invention is usually used as a composition dissolved in an organic solvent together with a suitable photosensitizer. In addition to the above-mentioned polar aprotic solvents, tetrahydrofuran and the like are preferably used as organic solvents for this purpose. Various solvents can be used without particular restriction as long as they do not impair workability. Furthermore, conventionally known photosensitizers can be used as appropriate. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzophenone,
Carbonyl compounds such as benzyl and benzyl dimethyl ketal, organic sulfur compounds such as benzyl sulfide,
Examples include certain halogen compounds and photoreducible dyes. However, it is not limited to these.

The photosensitizer is usually used in an amount of 0.01 to 7 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the photopolymerizable imide monomer.

Furthermore, the photocurable composition of the present invention may contain polymerizable monomers such as vinyl monomers, divinyl monomers, acrylic acid monomers, methacrylic acid monomers, and unsaturated polyester resins, if necessary. It may contain polymerizable resins such as, fillers, adhesion aids, etc.

The photocurable composition of the present invention can be used in the same manner as conventionally known ones, such as bar coaters,
After applying it to an adherend using an applicator, spinner, etc., it is photocured by irradiating it with ultraviolet rays to form a tough and heat-resistant film.

The photopolymerizable imide monomer according to the present invention has a cinnamoyl group that is sensitive to light in its molecule, so it has excellent photocurability, and as a photocurable composition in a solution state, it has excellent storage stability and scratches. Even if left at room temperature, it will not gel in a short period of time. In addition, it not only has excellent adhesion to adherends, but also has an imide group in the molecule, so after photocuring, it is a heat-resistant cured resin that satisfies all of the above properties. form.

Examples of the present invention are listed below, but the present invention is not limited to these Examples in any way.

Example 1 8.19 g (0,035 mol) of 1,2,3,4-butanetetracarboxylic acid and 1386 g (0,07 mol) and N-methyl-2-pyrrolidone (70 g) were charged and reacted at a temperature of 150 to 210° C. for 2 hours to obtain a solution of alcohol in N-methyl-2-pyrrolidone in the general formula.

Next, after cooling the temperature of this solution to 20°C, 11.66 g (0.07 mol) of cinnamic acid chloride and 10 g of triethylamine were added and dissolved therein, and the temperature was adjusted to a range of about 20 to 25°C. The reaction was carried out for 0.5 hours while maintaining the temperature. Thereafter, water was added to the reaction solution to obtain a photopolymerizable imide monomer according to the present invention as a precipitate, which was thoroughly washed.

10 g of this monomer was dissolved in 3 g of N-methyl-2-pyrrolidone, and further 0.3 g of benzophenone was dissolved.
A photocurable composition A was obtained.

Example 2 In a flask similar to Example 1, 1,2,3,4-butanetetracarvone #8.19 g (<0.035 mol), m-xylylenediamine 9.52 g (0.07 mol) and N - Prepare 70g of methyl-2-pyrrolidone, summer 30~
The mixture was reacted at a temperature of 200° C. for 3 hours to obtain a solution of Zenmin in N-methyl-2-pyrrolidone.

Next, after cooling the temperature of this solution to 20°C, 11.66 g (0.07 mol) of cinnamic acid chloride was added to it.
and 10 g of triethylamine were added and dissolved, and the mixture was reacted for 17 hours while maintaining the temperature in the range of about 20 to 23°C. Thereafter, water was added to the reaction solution to obtain a photopolymerizable imide monomer according to the present invention as a precipitate, which was thoroughly washed.

10 g of this single substance was mixed with 3 g of N-methyl-2-pyrrolidone.
A photocurable composition B was obtained by further dissolving 0.3 g of benzophenone.

Example 3 In a flask similar to Example 1, 8.19 g (0,035 mol) of 1,2,3,4-butanetetracarboxylic acid, 8.12 g (0,07 mol) of hexamethylene diamine, and hexamethylene phosphor were added. Prepare 70g of amide, 140~
The reaction was carried out at a temperature of 190°C for 3 hours to obtain a solution of N-methyl-2- and lolidone of i6 midoamine, where R = -(C11)- in the general formula.

Next, after cooling the temperature of this solution to 20°C, 11.66 g (0.07 mol) of cinnamic acid chloride was added to it.
and 10 g of triethylamine were added and dissolved, and the mixture was reacted for 7 hours while maintaining the temperature in the range of about 20 to 25°C.

Thereafter, water was added to the reaction solution to obtain a photopolymerizable imide monomer according to the present invention as a precipitate, which was thoroughly washed.

10 g of this monomer was dissolved in 3 g of N-methyl-2-pyrrolidone, and further 0.3 g of benzophenone was dissolved.
A photocurable composition C was obtained.

The following characteristic tests were conducted on the photocurable compositions A, B, and C thus obtained.

(11 Storage stability) Each composition was dissolved and mixed in N-methyl-2-pyrrolidone so that the imide monomer was 50% by weight, and the mixture was left at room temperature. No gelation occurred.

(2) Apply each photocurable composition on a 50 μm thick copper foil using a bar coater.
After coating to a thickness of 0μm, apply 8cm from a position 1Qcm away.
When the film was photocured by irradiation with two 0 W/cm high pressure mercury lamps for 5 minutes, a film that was sufficiently dry and hardened to the touch was formed in each case.

(3) Adhesiveness 3 The coating film photocured as above was cross-cut into 21 squares, and adhesive tape (No. 2, manufactured by Nitto Electric Industry Co., Ltd.)
9) was pasted and peeled off, but out of 100 crosscuts,
The number of peeled pieces was 0 in all cases.

(4) Heat resistance The coating film photocured as described above was heated at a temperature of 150°C for 120 minutes and the condition of the coating film was observed. No abnormality was observed.

(5) Solder heat resistance After the coating film cured by lightning as described above was immersed in a solder bath φ at 260±5°C for 10 seconds, the condition of the coating film was observed, but in all cases, the coating film did not peel off. No abnormalities such as deterioration were observed.

(6) Moisture resistance The coating film photocured as described above was heated at 40°C and 90% R.
After being left under the conditions of H for 120 hours, the state of the coating film was observed, and no abnormality such as peeling or deterioration was observed in the coating film in any case.

4 (7) Chemical resistance After the coating film photocured as described above was immersed in each solvent of toluene, tetrahydrofuran, and ethanol at a temperature of 250°C for 1 hour, the state of the coating film was observed. No abnormality was observed in the coating film in this case either.

Patent applicant: Nitto Electric Industry Co., Ltd. 5

Claims (1)

[Claims] (11) A photopolymerizable 5-imide monomer represented by the general formula (wherein, R represents a divalent organic group). (2) R is a divalent aliphatic or aromatic group. The photopolymerizable imide monomer according to claim 1, which is an alicyclic hydrocarbon group.