JPH0384016A - Optically curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for coating and in the field of ink, providing coating films having excellent heat resistance and photo-setting properties, comprising a specific aromatic polyamide oligomer, maleimide derivative and a photopolymerization initiator. CONSTITUTION:(A) An aromatic polyamide oligomer shown by the formula [A is radically polymerizable unsaturated group (preferably unsaturated aromatic group); R is H, lower alkyl or lower alkenyl; R1 and R2 are bifunctional aromatic group; (n) is 1-15] is blended with (B) a maleimide derivative (e.g. N- phenylmaleimide) and (C) a photopolymerization initiator (e.g. benzyl dimethyl ketal or 1-phenyl-2-hydroxy-2-methylpropan-1-one) to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a photocurable resin that can be used particularly in the field of coatings and inks that require heat resistance.

[Prior Art] Particularly in the field of electronics, there is a significant demand for improved heat resistance, and efforts are being made in various fields.

Attempts to use photocurable polyimide resins to improve the heat resistance of inks and coating resins used for various purposes, including resist inks, are well known.

In this case, a polyamic acid having a (meth)acryloyl group is photocured, and then heated to form a polyimide, and at the same time, the (meth)acryloyl group is decomposed and removed.

For this reason, it seems that there is still no ink resin or coating resin that has sufficient heat resistance for practical use through photocuring alone.

[Problem to be solved by the invention 1] As the demand for the plastic industry becomes more sophisticated, industrial materials with special properties are required, and this trend is rapidly developing as technology becomes more sophisticated. be.

The demand for improved heat resistance is felt in plastics, films, fibers,
Adds heat resistance to industrial materials in fields that require heat resistance, such as laminates, laminates, and adhesives.

This is also to expand the market and expand into a wide range of new fields with new capabilities.

In response to these demands, a group of synthetic resins called engineering plastics, such as aromatic polyamides, polyimides, polysulfones, and polyphenylene oxides, have already been developed and are now being industrialized as plastics with new functions different from conventional synthetic resins. Aromatic polyamides, known under the name aramid, are one of them, and are now being produced and opening up new areas of demand.

Representative types of aromatic polyamides include polyparaphenylene terephthalamide (product name: Kevlar) and polymetaphenylene isotucramide (product name Ninomex or HT-1) developed by Du Bont. .

All of these polyamides are classified as thermoplastic synthetic resins, and they generally have a high melting point, and the difference between the melting point and the thermal decomposition temperature is small, so melt molding may be difficult, but depending on the structure, it may be impossible. There was a problem. On the other hand, a type of polyamide that thermosets oligomers has not yet been found.

The reason why there was no thermosetting aromatic polyamide was as follows.
- This is thought to be due to the fact that the melting point was sufficiently higher than that of conventional thermoplastic synthetic resins, and the introduction of unsaturated bonds was considered to have a high risk of causing undesirable gelation during the molding process. .

On the other hand, it is also well known that one of the typical heat-resistant resins is a polymer formed by adding amino groups to unsaturated bonds in the Michael reaction of simalimides and aromatic diamines ( "Kelimide" by Ni Rhône-Boulin, France).

However, when attempting to homopolymerize maleimides, the polymerization reaction is too vigorous at high temperatures, making it impossible to obtain useful polymers.

[Means for Solving the Problems] The present inventors have developed an ink or coating material that is easily soluble in a solvent or a solvent, easily photocurable, has sufficient heat resistance after curing, and has an 81 machine The results of various studies to obtain an unsaturated polyamide oligomer with high physical strength and chemical stability.

(a) A photocurable composition comprising an aromatic polyamide oligomer represented by the formula % [1] (b) a maleimide derivative and (c) a photopolymerization initiator can be developed. The invention was completed.

The aromatic polyamide oligomer having a terminal unsaturated group according to the present invention can be illustrated by the following reaction formula.

(Margin below) (Aromatic dicarboxylic acid cybalide) (Aromatic polyamide oligomer) In order to allow the reaction [A] above to proceed smoothly.

A receptor for the by-produced hydrogen chloride is required, and for boat fishing it is convenient to use an aliphatic tertiary amine or a caustic alkali.

In this case, n is approximately 0 to 15 (however, when n = 0, aromatic dicarboxylic acid civalide is not used), and preferably a value of approximately 3 to 7 is advantageous from the viewpoint of ease of moldability. Polymerization is not particularly necessary.

This reaction is generally carried out by mixing amines in an aqueous phase and acid chlorides in an inert organic solvent that does not dissolve in water to perform an interfacial polycondensation reaction, or by dissolving both in an inert organic solvent and condensing them at low temperatures. It can be carried out by low temperature solution polycondensation reaction.

Aromatic amines having a terminal unsaturated group that can be used in the present invention include 0-aminostyrene, m-aminostyrene, p-aminostyrene,
-aminostyrene, m-isopropenylaniline, p-
Examples include isopropenylaniline, but m-aminostyrene and p-aminostyrene are suitable in terms of photocurability and heat resistance.

Further, as the aromatic dicarboxylic acid civalide that can be used in the present invention, dichlorides of aromatic dibasic acids are convenient, and representative examples include terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride, or mixtures thereof.

From a practical point of view, phthalic acid dichloride has insufficient heat resistance as aramid after curing, and terephthalic acid dichloride has sufficient heat resistance, but the resulting aromatic polyamide oligomer has a high melting point. Therefore, isophthalic acid dichloride best meets the purpose of the present invention.

This synthesis reaction proceeds relatively stoichiometrically, so after calculating n in the above formula [■], the necessary amounts of terminally unsaturated organic acid halide, aromatic diamine, and aromatic dicarboxylic acid civalide are added. If precise adjustment is required, the molar ratio can be determined by a simple test.

Examples of the aromatic diamine include metaphenylene diamine, 4.4°-diaminodiphenylmethane, and 4.4°-diaminodiphenylmethane.
Diaminodiphenylpropane, 3.3'-dimethyl-4
, 4′-diaminodiphenylmethane, 4.4°-diaminodiphenyl ether, 3.4°-diaminodiphenyl ether, 3.3°-diaminodiphenyl sulfone, 4
, 4°-diaminodiphenylsulfone, dianisidine,
2.4-) lylene diamine, 2.4/2.6-1
A mixture of -lylene diamine, 1,3-bis(3-aminophenoxy)benzene, etc. can be used for +lI, and a mixture of two or more types can also be used.

As already explained, the composition of the aromatic polyamide oligomer obtained by this reaction can be easily selected, and it can be molded by photocuring.

The aromatic polyamide oligomer having an unsaturated end group synthesized according to the present invention can be photocured in combination with a radical generating catalyst, making it possible to significantly improve heat resistance.

Maleimides used in combination with aromatic polyamide oligomers can be divided into the following three types.

+il phenylmaleimides (i it itit) The types of aromatic diamines synthesized from aromatic diamines and maleic anhydride are as described above.

(iii) Polymaleimide synthesized from aniline-formaldehyde condensate and maleic anhydride Furthermore, it is also possible to use a mixture of fil, (iii), and (iii).

Phenylmaleimide has a low melting point and wide compatibility with aromatic polyamide oligomers, but it also has a slight lack of heat resistance, so simalemides made from aromatic diamines are used between the shells.

Examples of these include N-phenylmaleimide, N-(
0-chlorophenyl)maleimide.

N,N'-diphenylmethane bismaleimide, N,N
' -Diphenyl ether bismaleimide, N, N'-
Paraphenylene bismaleimide, N.

N'-(2-methylmetaphenylene) bismaleimide,
N, N'-metaphenylene bismaleimide, N,
Examples include N'-(3,3°-dimethyldiphenylmethane)bismaleimide, maleimide of N, N'-(3,3°-diphenylsulformaldehyde condensate), and the like.

The aromatic polyamide oligomer (including terminal unsaturated organic acid amide of aromatic polyamine) used in the present invention has a slow photocuring speed, but by incorporating a maleimide derivative, the photocuring speed can be increased. can be improved.

The blending ratio of the aromatic polyamide oligomer and the maleimide derivative is 10 to 200 parts by weight of the maleimide derivative, preferably 10-1 to 100 parts of the aromatic polyamide oligomer.
00 parts by weight.

When the amount of maleimide added is 10 parts by weight or less, heat resistance is good, but the effect of improving photopolymerizability is small, and
When the amount is 0 parts by weight or more, there is a problem that heat resistance decreases.

The photopolymerization initiator used in combination with the aromatic poly7mide oligomer and the maleimide derivative is not particularly limited, and various commercially available types can be used as they are.

Examples of these are:

(a) Benzyl ethers (1) benzyl dimethyl ketals (c) acetophenone derivatives (2) combinations of benzophenone and tertiary amines (main) benzyls (f) combinations of thioxanthone and tertiary amines (g) acylophosphine oxy Examples include the following.

From the viewpoint of availability and photo-curing ability, benzyldimethylkecur (Ciba Corporation "Irgacure #651" l), acetophenone derivative (l-phenyl-2-hydroxy-2-
Methylpropan-1-one: Merck “Darocur #”
1173”) is useful.

The ratio of photoinitiator used is 100 parts of the unsaturated aramid oligomer and maleimide derivative mixture to 1 part of the mixture. O. l
- 10 copies.

The unsaturated aromatic polyamide oligomer and maleimide derivative mixture is dissolved in a solvent or a soluble monomer and used in liquid form.

It can be used as is in the form dissolved in nanatsuma.

In the case of a solution dissolved in a solvent, the solvent is evaporated and used.

It goes without saying that the composition of the present invention may contain filler colorants, thickeners, antifoaming agents, mold release agents, and polymers, if necessary.

Next, examples will be shown below to help understand the present invention.

[Example] (Oligomer [I]) lil equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer
20.3 g (0.1 mol) of isophthalic acid chloride and 100 g of dimethylformamide (DMF) were placed in a four-neck separable flask and cooled to below 10°C.

Next, 16°7 g of 3.4°-diaminodiphenyl ether
(0,0834 mol), triethylamine 16.87
g (0,167 mol), 75 g of DMF in 19 it
21 and dropwise into a separable flask.

Next, 3.97g of p-aminostyrene (0°0333
mol), 3.33 g (0,0333 mol) of triethylamine, and 25 g of DMF were weighed and mixed and added dropwise to a separable flask. During this time, the temperature of the mixture was maintained at 10° C. or less. After the completion of the 0 dropwise addition, stirring was continued at the same temperature for 2 hours.

The reaction mixture is then gradually added to vigorously stirred water to allow crystals to precipitate. The precipitated crystals are suction filtered, washed with water, and then dried.

m, p, 180-192°C (Synthesis Example 2) (Hereafter the margin) (Oligomer [111) 2. instead of 3.4°-diaminodiphenyl ether.
10.17 g (0,0834
The same operation as in Synthesis Example 1 was performed except that mol) was used.

m, p, 190-205°C (Synthesis Example 3) (Oligomer [■]) 3. instead of 4°-diaminodiphenyl ether.
20.67 g of 3°-diaminodiphenylsulfone (0,
The same operation as in Synthesis Example 1 was performed except that 0833 mol) was used.

m, p, 145-160℃ (Example 1) Oligomer [I] obtained in Synthesis Example 1 5 g, N.

No-diphenylmethane bismaleimide 5g, DMF5
g, tetrahydrofuran 7g, Darocure #1173 (
Merck Co., Ltd., photopolymerization initiator) 0.2g was weighed, 30+n
Add to j2 Erlenmeyer flask First, put in an ultrasonic cleaning tank and stir to dissolve.

The uniformly dissolved resin liquid was placed on a 35 μm thick electrolytic copper foil for 5 minutes.
After coating to a thickness of 0 μm, it was heated at 80°C for 1 hour.
The mixture was heated at 30° C. for 1 hour to remove the solvent and dry.

At this stage, it was confirmed that the coating film on the copper foil obtained was soluble in DMF and was not cured.

The coating film on this copper foil was exposed to the bottom of an ultraviolet irradiation device with an output of 2KW.
cm at a speed of 1 m/min.

The coating film was cured, had a hardness of 3H, and no dissolution, swelling, or peeling was observed even after immersion in DMF for 30 minutes.

Also, it did not peel off even if it was left on a 260℃ solder bath for 60 seconds.
*No phenomena such as shrinkage or shrinkage occurred, and no abnormality of the coating film was observed.

(Example 2) Oligomer [II] obtained in Synthesis Example 2 was used instead of oligomer [I], and other conditions were the same as in Example 1, and ultraviolet irradiation, dissolution test, and solder heat resistance test were conducted.

The results were similar to Example 1.

(Example 3) Oligomer obtained in Synthesis Example 3 [■! ], 3 g of N-phenylmaleimide, 5 g of DMF, 5 g of methyl ethyl ketone
g, Darocure al173 (manufactured by Merck & Co., photopolymerization initiator) 0.2 g were weighed and added to a 30 mj2 Erlenmeyer flask.

Next, put it in an ultrasonic cleaning tank and stir to dissolve. After coating the uniformly dissolved resin liquid on a 35 um thick electrolytic copper foil to a thickness of 50 μm, it was heated at 80°C for 1 hour and at 120°C for 2 hours.
After heating for a period of time to form a coating film, it was passed 10 cm below an ultraviolet irradiation device with an output of 2 kW at a speed of 1 m/min.

The coating film was cured, had a hardness of 2 to 3H, and no dissolution or swelling was observed even after immersion in DMF for 30 minutes.

Further, even though it was left on a 260°C solder bath for 60 seconds, no phenomena such as peeling or blistering were observed.

(Example 4) The test was carried out under the same conditions as in Example 1 except that the sample was passed through one oan under the ultraviolet irradiation device with an output of 2 kW at a speed of 2 m/min.

The coating film was cured, had a hardness of 3H, and no dissolution, swelling, or peeling was observed even after immersion in DMF for 30 minutes.

(Comparative example) Aromatic polyamide oligomer [I] obtained in Synthesis Example 1 instead of 5 g of N,N'-diphenyl bismaleimide 5
The experiment was carried out under the same conditions as in Example 4 except that g was added.

The paint film was cured, but swelled after being immersed in DMF for 30 minutes.
Some peeling was observed.

[Effect J] The photocurable composition of the present invention can be used as an ink or coating composition that has a high degree of heat resistance, and in particular can be blended with a maleimide derivative without impairing the heat resistance characteristic of aromatic polyamides. This material has significantly improved photocurability, and is expected to be used in fields that require heat resistance, such as electronics and painting.

Claims (2)

[Claims] (1) (A) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼...[I] [However, in the formula, A is a radically polymerizable unsaturated group, and R is a hydrogen atom, lower alkyl group, or lower alkenyl group. , R_1
, R_2 is a group selected from the group consisting of divalent aromatic groups (
n=any numerical value from 1 to 15). A photocurable composition comprising an aromatic polyamide oligomer represented by (b) a maleimide derivative and (c) a photopolymerization initiator. (2) The photocurable composition according to claim (1), wherein the radically polymerizable unsaturated group is an unsaturated aromatic group.