JPS5813657A - Curable resin composition having excellent heat resistance - Google Patents

Abstract

PURPOSE:To prepare the titled liquid composition having remarkably improved curing rate and workability without lowering the heat resistance of the resultant cured product, by compounding trismercaptopropyl isocyanurate to a specific unsaturated esterimide compound. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of an unsaturated esterimide compound having imide bond and crosslinkable ethylenic double bond in the main chain of the molecule and hydroxyl groups or carboxyl groups at both terminals of the molecule and (B) 20- 50pts.wt. of the compound of formulaI. The compound of the component (A) can be prepared by the condensation reaction of (i) an acid component composed of an imide group-containing dibasic acid of formula II or formula III (X is trivalent organic group; Y and Q are bivalent organic group) and a dibasic acid having crosslinkable ethylenic double bond and (ii) a polyol. The compounded composition is liquid or semisolid at normal temperature, and can be applied at normal temperature or by moderate heating, and the coating film can be cured with radiations.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to a curable resin composition having good heat resistance, which can be crosslinked by radiation such as ultraviolet rays, and can optionally be cured by heat shrinkage.

In recent years, there has been a high demand for curable materials, especially materials that can be rapidly cured by radiation such as ultraviolet rays (mainly used as protective materials, insulating materials, solder resists, adhesives, coating materials, etc. in the electrical and electronic fields). It is also being applied as a heat-resistant photoresist in semiconductor devices.

This type of curable material is required not only to be radiation curable or thermosetting and to have excellent heat resistance during curing, but also to be resistant to the adherend. It is desirable that the material exhibits good adhesion and also satisfies other properties such as insulation properties, moisture resistance, and chemical resistance. On the other hand, from the viewpoint of pollution-free, resource-saving, and energy-saving, it has the ability to form a film without solvent or with a small amount of solvent, and furthermore, the curable material in such a state gels over time before use. It is desired that the product has excellent storage stability without causing any problems. However,
The reality is that almost no conventional curable materials, particularly radiation curable materials, that satisfy all of these required properties have been found.

By the way, in the course of many years of research into this type of material, the inventors introduced an imide bond and an ethylenic double bond into the main chain of the molecule, and left hydroxyl or carboxyl groups at both ends of the molecule. A specific unsaturated esterimide compound that is cured by radiation such as ultraviolet rays has good heat resistance, insulation properties, moisture resistance, chemical resistance, etc., and is storage stable when stored in a solution state before curing. It has already been found that it can be a very suitable material.

However, according to subsequent research by the inventors, the above-mentioned specific unsaturated esterimide compounds are generally solid or semi-solid at room temperature, and when used without a solvent or with a small amount of solvent, they melt. A heating means such as coating is required, and even if such heating means is applied, a beautiful finished surface may not be obtained in some cases. Such problems can usually be avoided by using the required amount of organic solvent, but in this case, there is a risk that resource and energy conservation problems will arise due to the use of a large amount of organic solvent.

On the other hand, it is often possible to improve the handling and workability of the curable material by blending a liquid compound in the form of an i. It is being done. Such liquid compounds include ethylene glycol diacrylate monomers,
Divinyl compounds such as divinylbenzene, diacryl phthalate, diallyl isophthalate, and general vinyl monomers are known.

Based on the same idea as above, the inventors initially attempted to blend the above-mentioned general liquid compound with the above-mentioned specific unsaturated esterimide compound. However, although this type of liquid compound can improve the handling properties as a curable material, it has the drawback of decreasing heat resistance during curing.
There was a concern that this would impair the excellent heat resistance, which is one of the characteristics of unsaturated esterimide compounds.

In light of the above-mentioned circumstances, this invention has been made through further studies and has led to the discovery of a suitable liquid compound that can greatly improve the curing speed and workability during use without impairing the heat resistance of curing. It was completed based on knowledge.

That is, the present invention provides an unsaturated ester imide compound having an imide bond and a crosslinkable ethylenic double bond in the main chain of the molecule, and a hydroxyl group or a carboxyl group at both ends of the molecule, and trismercaptopropyl isocyanurate. The present invention relates to a curable resin composition having excellent heat resistance.

As described above, the curable resin composition of the present invention is one in which trismercaptopropyl isocyanurate is blended with the above-mentioned unsaturated esterimide compound, and according to this, no or almost no organic solvent is used. It is possible to obtain a liquid or semi-solid composition at room temperature, and this composition can be applied at room temperature or by heating to a certain extent, so the workability during use is greatly improved. Become.

In addition, the above-mentioned coating can be cured by radiation such as ultraviolet rays or by heat treatment in some cases, but this curing reaction is caused by the crosslinkable ethylenic double bonds contained in the unsaturated esterimide compound. The polymerization reaction between the above double bond and the mercapto group (-8R) of trismercaptopropyl isocyanurate is the main one, rather than the secondary reaction of polymerization itself. Although the reaction uses a radical polymerization mechanism like the former, it is hardly affected by the polymerization inhibiting effect of oxygen in the air, and is therefore characterized in that the overall curing rate is extremely fast.

Moreover, the product cured in this way shows no decrease in heat resistance due to the incyanurate ring contained in trismercaptopropyl isocyanurate, and has excellent heat resistance that is almost comparable to that of the unsaturated esterimide compound alone. The above-mentioned isocyanurate compound has three mercapto groups and exhibits relatively good flexibility despite having a high crosslinking density. In addition, it has a beautiful surface appearance due to the improved coating workability, and has excellent insulation properties and
It also has excellent general properties such as moisture resistance and chemical resistance.
Furthermore, it has sufficient storage stability when stored in liquid state before use! /ζ°ru.

By the way, some conventionally known photosensitive materials contain (
Unsaturated oligomers with meth)acryloyl or allyl groups and pentaerythritolpropane tris(β
-Mercaptopropionate), ethylene glycol dimercaptopropionate, and other polythiols, and a method is known in which this is irradiated with ultraviolet rays and polymerized and cured by reaction between the polyene and mercapto group. However, this cured product was extremely poor in heat resistance and had a very strong odor from the raw material polythiol, making it lacking in industrial utility.

On the other hand, although the trismercaptopropyl isocyanurate used in this invention is a type of polythiol, it has a high boiling point and high vapor pressure, so it is difficult to handle it during coating work etc.
Even after being cured with an unsaturated polyesterimide compound, it has a weak odor and provides a cured product with essentially no heat resistance, and in this respect as well, it can be said to be an extremely useful curable material industrially.

The unsaturated ester imide compound used in this invention has an imide bond and a crosslinkable ethylenic double bond in the main chain of the molecule, and a hydroxyl group or a carboxyl group at both ends of the molecule. The compound can be produced by various methods such as those described below.

The first method is to synthesize a tribasic acid containing an imide group (hereinafter simply referred to as imidic acid *4), and a tribasic acid having an ethylenic double bond that can be crosslinked with this (hereinafter simply referred to as imidic acid). This is a method in which a polybasic acid (referred to as a crosslinking tribasic acid) is used in combination, and these are used as a polybasic acid component to undergo a condensation reaction with a polyol.

Typical imide acids are illustrated by the following general formula tl
), +21, +3).

(In each formula, X is a trivalent organic group, Y and q are a divalent organic group, and Z is a tetravalent organic group) The imidic acid having the structure represented by the above general formula (1) is as follows: 1 mol of tricarboxylic acid anhydride represented by the general formula (4); (X is the same as above) and the following general formula (5); % formula % (51 (Y is the same as above) It can be synthesized by reacting with 1 mole of the aminocarboxylic acid represented by the formula.The reaction is generally carried out in the presence of an appropriate organic solvent such as cresol, and the amount of one of the raw materials is slightly larger than the theoretical mole number above. There is no problem.

The tricarboxylic acid anhydride used here includes, for example, trimellitic anhydride, 3,4,4'-diphenyl ethertricarboxylic acid anhydride, ethylenetricarboxylic acid anhydride, 2,3,6'-naphthalene tricarboxylic acid anhydride, Examples include anhydrides. Typical examples of the aminocarboxylic acid represented by formula 15) include P-aminobenzoic acid, m-aminobenzoic acid, γ-aminobutyric acid, anthranilic acid, and β-aminopropionic acid.

Further, the imidic acid having the structure represented by the general formula (2) is a tricarboxylic acid anhydride 2 represented by the above general formula (4).
Mol and the following general formula +61, (71:H2N-Q-
NO3...(6) OCN-Q-NCO...(7) (Q is the same as above) It can be synthesized by reacting with 1 mol of diamine or diisocyanate represented by the following formula. The reaction is generally carried out in the presence of a suitable organic solvent such as cresol, and the amount of one of the raw materials may be slightly larger than the theoretical mole number mentioned above.

The tricarboxylic acid anhydride used here is the same as mentioned above, but the diamines include diaminodiphenylmethane, diaminodiphenyl ether, m-phenylenediamine, 0-phenylenediamine, P-phenylenediamine, 4e4' -Phenyl, 4,4'-diaminobenzophenone, 2,4-toluenediamine, 2
・6-Toluene diamine, hexamethylene diamine, ethylene diamine, xylylene diamine, diaminopropane, etc. can be mentioned. Further, as the diisocyanate, the same organic group (Q) as the diamine described above can be used in the same manner.

Furthermore, the imidic acid having the structure represented by the general formula (3) is
Tetracarboxylic dianhydride represented by the following general formula (8); (Z is the same as above), or 1
- Tetracarboxylic acids such as 2,3,4-butanetetracarboxylic acid 1. It can be synthesized by reacting 2 moles of the aminocarboxylic acid represented by the general formula (5) with 2 moles of the aminocarboxylic acid represented by the general formula (5). The reaction is generally carried out in the presence of a suitable organic solvent such as N-methyl-2-pyrrolidone, and the reaction may be carried out using one of the above raw materials in an amount slightly larger than the theoretical mole number.

The aminocarboxylic acid used here is the same as above, but specific examples of the tetracarboxylic dianhydride represented by the general formula (8) include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3. 3'・4・4'-
Diphenyltetracarboxylic dianhydride, 2, 2', 3,
3'-diphenyltetracarboxylic dianhydride, 2.3.
6,7-naphthalenetetracarboxylic dianhydride, 2,2
'-His(3,4-dicarboxyphenyl)furopannianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and the like.

The crosslinkable tribasic acid used together with such imide acid has at least one crosslinkable ethylenic double bond in its molecule, and the above ethylenic double bond is the non-reactive component of the photosensitizer. Depending on whether the acid is sensitive to light such as ultraviolet rays in the presence of light, tribasic acids with relatively low photosensitivity (hereinafter referred to as group A crosslinking acids) and tribasic acids with high photosensitivity acids (hereinafter referred to as group b crosslinking acids).

Specific examples of group a crosslinking acids include maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, diphenylmethane-diγ-crotonic acid-4 and 4. (HOOC-CH
=CH-CO-Ph-CO-CH=CH-COOH(P
h is a phenyl group)]. Also, b
Specific examples of group crosslinking acids include P-phenylene diacrylic acid, m-phenylene diacrylic acid, 4-carboxycinnamic acid, 3-carboxycinnamic acid, cinnamylidenemalonic acid, and derivatives thereof. Can be mentioned.

These crosslinking tribasic acids may be used by selecting one or more types from either group a or group b crosslinking acids, or selecting two or more types from both groups a and b. You can use it. The proportion of such crosslinking tribasic acid used is:
It is usually 10 to 95 mol %, preferably 60 to 90 mol % of the total amount with the above-mentioned imide acid. However, the optimum proportion used varies somewhat depending on the structure of the imidic acid and the type of crosslinkable tribasic acid. In any case, it is necessary that the crosslinking tribasic acid be used in an appropriate proportion to the imidic acid; if the amount of the tribasic acid used is too small, the curing speed will be slow, making it impractical. Also, if the amount is too large, the amount of imide acid used will decrease accordingly, resulting in a loss of heat resistance.

The polybasic acid component used in the first method consists of the above-mentioned imide acid and crosslinking tribasic acid, but in addition to these acid components, non-crosslinking It may be used in combination with other tribasic acids. Such non-crosslinking tribasic acids are used for the purpose of finely adjusting crosslinking and curing properties, so if too much is used, heat resistance, curability, and other general properties may be impaired; It is desirable that the amount is 30 mol or less based on the total polybasic acid component.

Specific examples of the non-crosslinking tribasic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, 3,6-nindomethylenetetrahydrophthalic acid, tetrachlorphthalic anhydride, 3,6 - Aromatic, aliphatic or alicyclic tribasic acids such as dichloromethylenetetrachlorophthalic acid, tetrachlorophthalic acid, adipic acid, sepathic acid, thiodiglycolic acid, or their derivatives are widely used. Included.

Diols are generally used as the polyols to be reacted with the polybasic acid component, but in some cases, tri or more polyols may be used together with the diols. Specific examples of these include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, cyclohexane jetanol, hydrogenated bisphenol A, 1.4-butanediol, 1.5-bentanediol, Examples include diols such as hexamethylene glycol, glycerin, triols such as tris(hydroxyalkyl)in cyanurate, and the like.

Condensation reaction between a polybasic acid component and polyols: Normally, polyols are used in excess and reacted by heating, then unreacted polyols are distilled off under reduced pressure, and the resulting mixture is heated and reacted to achieve a high degree of condensation. done in a method. In this case, a method may be adopted in which one of the polybasic acid components, imide acid or crosslinking tribasic acid, is reacted with a polyol, and then the remaining acid component is added thereto and the reaction is carried out by heating. You can also do it.

The first method described above is particularly recommended as a general method for producing the unsaturated ester imide compound of the present invention, but its drawback is that cresol, N-
It requires an organic solvent such as methyl-2-pyrrolidone. Therefore, if you wish to avoid the use of such organic solvents, please follow the second method below. A third method may also be adopted.

The second method is based on the general formula (i+, (21, (31
Without pre-synthesizing the imide acid represented by the general formula +4+ , +
First, the acid component represented by 81, etc., the crosslinking tribasic acid and, if necessary, other non-crosslinking dibasic acid are reacted with polyols to synthesize a predetermined polyester, and then the general formula +51, This is a method in which an amide 7 group-containing compound represented by +61 is added to perform an imidization reaction and a condensation reaction.

In this second method, the use of organic solvents can be avoided by using an excess of polyols during the synthesis of the polyester, and the synthesized polyester is melted by heating in the presence of an excess polyol. In order to maintain this state, a homogeneous reaction can be carried out by adding an amino group-containing compound to this.

In addition, the third method does not involve pre-synthesizing imidic acid in the same way as the second method described above. +51, the amine group-containing compound represented by (6), the crosslinking tribasic acid, other non-crosslinking tribasic acid if necessary, and polyols are simultaneously charged into a reactor and condensed at once. This is a method of carrying out reactions and imidization reactions.

Also in this method, the use of organic solvents can be avoided by using an excess of polyols.

Note that the ratio of each raw material used in the second and third methods is the same as in the first method. Also,
In the second and third methods, diincyanate represented by general formula (7) is excluded as an imidization reagent, but
This is because when diisocyanate is used, urethane bonds are mainly formed, which causes a decrease in heat resistance.

The unsaturated ester imide compound of the present invention produced in this way does not necessarily have a constant molecular structure depending on the various reaction forms and number of reaction moles described above, but at least it contains imide acid in the main chain of the molecule. It has an imide bond derived from (or is finally formed from its synthetic raw material) and a crosslinkable ethylenic double bond derived from a crosslinkable tribasic acid, and has free at least at both ends of the molecule. It has a carboxy group or a hydroxyl group, the hydroxyl value is usually 0.2 to 1.5 mil J, and the acid value is usually 1.0 mil. It is solid or semi-solid at room temperature with j equivalent/V or less.

If the above hydroxyl value becomes too low, even if pyruisocyanurate is added, it will not be effective in reducing the viscosity and it will be difficult to improve workability during use.On the other hand, if it is too high, the product will have a low molecular weight. When cured, properties such as chemical resistance and flexibility are likely to be adversely affected. Furthermore, if the acid value becomes too high, problems mainly arise in moisture resistance, alkali resistance, etc.

In this invention, it is important to blend trismercaptopropyl isocyanurate as a liquid compound into the unsaturated esterimide compound as described above. A liquid or semi-solid curable resin composition is obtained.

The above trismercaptopropyl isocyanurate is
It has a low viscosity of about 53 poise at room temperature (25°C), expressed by the following formula: %.

The proportion of trismercaptopropylisocyanurate to be used is preferably 0.3 to 2 equivalents, preferably 1 equivalent or less, relative to the ethylenic double bond contained in the unsaturated esterimide compound. . Expressed in parts by weight, it is generally an unsaturated ester imide compound of 100
It is 5 to 70 parts by weight, preferably 20 to 50 parts by weight. If the proportion used is too small, the effect of using this compound cannot be obtained sufficiently, and if it is too large, problems will arise in heat resistance after curing.

The thus obtained curable resin composition of the present invention is resistant to radiation such as ultraviolet rays due to the crosslinkable ethylenic double bond contained in the molecular main chain of the unsaturated esterimide compound and the mercapto group of trismercaptopropyl isocyanurate. It can be rapidly cured by wire or, if necessary, it can be cured by heating.

In the ultraviolet ray-curable vine resin composition which is a particularly preferred embodiment of the present invention, a sensitizer such as a photosensitizer is added to 100 parts by weight of the unsaturated esterimide compound.
~20 parts by weight can be blended. Since the reaction between the crosslinkable ethylenic double bond and the mercapto group contained in the unsaturated esterimide compound in this invention is fast, even if the double bond is derived from the group A crosslinking acid, the reaction with the mercapto group is rapid. It is possible to photocure well without the aid of a sensitizer, but it is desirable to use a photosensitizer to further speed up the curing rate. Further, when the E double bond is derived from a group 5 crosslinking acid, a photosensitizer is not necessary, but it goes without saying that it may be used depending on the purpose of use.

Examples of the above photosensitizer include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzyl, carbonyl compounds such as benzyl dimethyl ketal, organic sulfur compounds such as benzyl sulfide, halogen compounds, and photoreducible dyes. It is also possible to use spectral sensitizers such as N-acetyl-4-nitronaphthylamine and 5-double P ayanaphthene.

In addition to the above-mentioned sensitizer, such a resin composition that can be cured by ultraviolet rays may optionally contain a known organic peroxide as a thermosetting catalyst. When such a peroxide is blended, the effect of improving the curing function can be obtained by first curing with ultraviolet rays and then further post-heating treatment.

Examples of such organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, and te
Examples include rt-butylperoxylzoate and dicumyl peroxide. The proportion used should be 5 parts by weight or less per 100 parts of the unsaturated esterimide compound! I'm bored.

Next, in one embodiment of the present invention, which is a thermosetting resin composition that can be cured by heat treatment, an organic peroxide is generally used as a thermosetting catalyst as described above, and an organic peroxide is used as a thermosetting catalyst. The amount is usually 0.5 to 5 parts by weight per 100 parts by weight of the saturated ester imide compound.

As mentioned above, the curable resin composition of the present invention may contain a photosensitizer, an organic peroxide, etc. depending on whether it is ultraviolet curable or thermosetting. In addition to these ingredients, by adding a maleimide compound or triallylisocyanurate as a curable subcomponent, it is possible to further improve the heat resistance of the cured product or reduce the viscosity, thereby further improving coating workability. can.

Typical examples of the above maleimide compounds include monomaleimides represented by the following general formula; (R is hydrogen, an alkyl group, or a phenyl group, and R2 is a -valent organic group); ;(R□
is the same as above, and - is a divalent organic group).

The monomaleimide represented by the general formula (9) is R in the formula
2 is preferably an alkyl group, an aryl group, an aralkyl group, or a halogen-substituted product thereof, for example,
N-phenylmaleimide, N-P-toluylmaleimide, N-m-)ruylmaleimide, N-α-naphthylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
N-butylmaleimide, N-hexylmaleimide, N-
Examples include octylmaleimide, N-dodecylmaleimide, 2-methylethylmaleimide, 2-phenylphenylmaleimide, and 2-methylphenylmaleimide.

The general bismaleimide represented by 2〇〇 is preferably an alkylene group, an arylene group, or an aralkylene group, such as N, N-p-phenylene bismaleimide, NeN'-m-phenylene bismaleimide, N-N'-(oxy-P-phenylene) bismaleimide, N,N'-(methylene-P-)22-)bismaleimide, N-N'-(methylene-P-
phenylene)bis[2-methylmaleimide), N-#-
(methylene-di-P-phenylene)bis[2-phenylmaleimide], N-N'-2,4-tolylenebismaleimide, N-N'-2,6-tolylenebismaleimide, N
-N'-m-xylylene bismaleimide, N-N'-P
-xylylene bismaleimide, N-N'-oxypropylene bismaleimide, N,N'-ethylene gas [oxypropylene bismaleimide F:), l1l11. N'-oxydiethylenebismaleimide, N,N'-ethylenebismaleimide, N,N'-ethylenebis[2-methylmaleimide], N-mertrimethylenebismaleimide, N
-N'-tetramethylene bismaleimide, N-hexamethylene bismaleimide, N-N'-hexamethylenebis[2-methylmaleimide], N-,*-dodecamethylene bismaleimide, and the like.

It is best to use 0 to 40 parts by weight of citriallylisocyanurate, which is not a bismaleimide compound, per 100 parts by weight of the unsaturated ester imide compound; if too much is used, the characteristics of the unsaturated ester imide compound may This is not desirable because it will be damaged. In addition, when using these compounds, the amount of trismercaptopropyl isocyanurate to be used should be determined in consideration of the number of ethylenic double bonds contained therein. That is, the mercapto group of trismercaptopropyl isocyanurate generally has the above-mentioned equivalent, preferably 1 equivalent to It is desirable to set the usage ratio to be less than that.

In addition to the above, the curable resin composition of the present invention may contain known additives such as fillers and adhesion aids, as well as ethanol, toluene, acetone, and tetrahydrofurane to finely adjust the amount depending on the purpose of use. . Furthermore, the viscosity of the composition can be further reduced by blending liquid compounds such as general vinyl monomers, divinyl compounds, and unsaturated polyester resins in proportions that do not impair the properties of the cured product.

When using the curable resin composition of this invention,
Since this is in a liquid or semi-solid state at room temperature, it can be coated on an adherend using a bar coater, applicator, or spinner, either as it is at room temperature or with slight heating. By irradiating the cured film with heat treatment if necessary, a cured film having a beautiful surface appearance and excellent properties as described above can be formed.

Examples of this -'□light will be described below. In the following, the terms "part" and "%" refer to "part" and "% by weight".

Example 1 In a four-hole flask with a partial condenser, 4.
198.f (1.0 mol) of 4'-diaminodiphenylmethane and 38412.0 mol of trimellitic anhydride were added, and further 1000 y- of N-methyl-2-pyrrolidone was added.
was added and stirred while blowing nitrogen gas, and the temperature was increased from room temperature to 1.
After raising the temperature to 50°C, a heating reaction was carried out at 150 to 160°C for 2 to 3 hours. The contents of the reactor were poured into a large amount of ethanol to precipitate the imide acid having the structure represented by the general formula (2), which was filtered and thoroughly washed with methanol, and then dried under reduced pressure at 100°C.

This imidic acid 66.3F (0.15 mol), fumaric acid 9
8.6y (0,85 mol) and ethylene glycol 3
10y (5 mol) was put into a fourth flask equipped with a partial condenser, stirred well while blowing nitrogen gas, and after raising the temperature from room temperature to 190° C., it was heated and mixed for 8 hours. At that time, excess ethylene glycol was distilled off under reduced pressure, and in order to further increase the degree of condensation, approximately 4 mm HP
Heat condensation was carried out under reduced pressure at 200° C. for 3 to 4 hours. The unsaturated esterimide compound thus obtained has a hydroxyl value of 0.55 miIJ equivalent/f! It had an acid value of 0 and was semi-solid at room temperature.

To 100 parts of this unsaturated ester imide compound, 35 parts of trismercaptopropylisocyanurate and 6△ parts of penzoylsopropyl ether were blended and melt-mixed to obtain the photocurable resin composition of the present invention. . This composition was liquid at room temperature and had a viscosity of 272 voids at 30°C.

Example 2 Unsaturated esterimide compound 100 obtained in Example 1
25 parts of trismercaptopropyl isocyanurate, 20 parts of triallylisocyanurate, and 6 parts of benzoyl isocyanurate were blended and melt-mixed to obtain the photocurable resin composition of the present invention. This composition was liquid at room temperature and had a viscosity of 225 poise at 30°C.

Example 3 Unsaturated esterimide compound 100 obtained in Example 1
35 parts of trismercaptopropyl isocyanurate, 5 parts of N-N'-(methylene-di-p-phenylene) bismaleimide, and 6 parts of benzoyl isopropyl ether are blended and melt-mixed to produce the present invention. A photocurable resin composition was prepared. This composition is liquid at room temperature, and
The viscosity at 0°C was 305 poise.

Comparative Example Unsaturated esterimide compound 10 obtained in Example 1
(4 diacrylates of ethylene glycol for 1
0 parts and 5 parts of benzoyl isopropyl ether were blended and melt-mixed to obtain a photocurable resin composition. This composition was liquid at room temperature and had a viscosity of 180 poise at 30°C.

Reference Example Unsaturated esterimide compound obtained in Example 1 100
5 parts of benzoyl isopropyl ether was blended and melt-mixed to obtain a photocurable resin composition.゛This composition was semi-solid at room temperature.
9. , Coating workability, coating film α, and lamp output when each of the curable resin compositions of Examples 1 to 3, Comparative Examples, and Reference Examples described above were coated on copper foil to a thickness of 100μ. is l
Using two KW high pressure mercury lamps, 20C from the coating surface.
The results of examining the 10% weight loss temperature change of the cured product when it was photocured by irradiating it for 5 minutes from a distant position were as shown in Table 1 below.

As is clear from the upper table of Table 1, the curable composition of the present invention allows good coating work and satisfactorily satisfies heat resistance.

Further, from the results shown in Table 2 below, which tested the curable compositions of the Examples, Reference Examples and Comparative Examples, it can be seen that the compositions of the present invention are excellent in various general properties.

Table 2 (*1) Each composition was dissolved in N-methyl-2-pyrrolidone to form a highly concentrated solution, which was left at room temperature and changes in properties were observed with the naked eye.

(*2)...A photo-cured coating film with a coating thickness of 2 to 10μ and cured in the same manner as above was cross-cut into 2m squares, a cellophane tape was pressed onto it, and then rapidly peeled off. The number of peeled pieces in 100 crosscuts was investigated.

(*3)...When a copper foil with a photo-cured coating similar to that used in the adhesion test was immersed in a solder bath at 260±5°C for 10 seconds, abnormalities such as blistering and peeling were observed in the cured film. I checked to see if I could see it.

No abnormalities were evaluated as good, cases where slight abnormalities were observed were evaluated as somewhat good, and cases where abnormalities were observed were evaluated as poor.

(*4)...When a copper foil with a photocured coating similar to the one used in the adhesion test was left in an atmosphere of 90% RH for 120 hours, rusting of the copper foil and devitrification of the cured coating occurred. It was examined whether abnormalities such as the following were observed, and those with no abnormalities were evaluated as good, and those with abnormalities were evaluated as poor.

(*5)...For the same photo-cured coating film as in the adhesion test, when it was immersed in toluene, tetrahydrofuran, and ethanol for 1 hour at 25°C, the cured film blistered.
It was examined whether ρ abnormal phenomena such as peeling were observed, and cases where no abnormalities were observed were considered good, and cases where abnormalities were observed were judged to be poor.

Example 4 134.4 fI (0.7 mol) of trimellitic anhydride and fumaric anhydride were placed in a four-bottle flask equipped with a partial condenser.
75.4 f (0.65 mol) and ethylene glycol 1s6Si (3 mol) were charged, stirred while blowing nitrogen gas, and heated from room 11゛1λ to 200°C for 6 hours at 200°C. The reaction was carried out by heating.

Next, diaminodiphenylmethane 69.3P (0°3
5 mol) and further imidization reaction for 3 hours.
Heat condensation was carried out at 200° C. for 2 hours under reduced pressure of about 4 mmHg. The unsaturated 5',..., esterimide compound thus obtained has a hydroxyl value of 0.62 milliequivalents/P and an acid value of 0.03 milliequivalents! J equivalent/V, and was solid at room temperature.

The compound was added to 100 parts of this unsaturated esterimide compound and melt-mixed to obtain a photocurable resin composition of the present invention. This composition is liquid at room temperature and has a viscosity of 115 at 30°C.
It was Poise.

Example 5 In a fourth flask with a partial condenser, trimellitic anhydride 79.2 F (0.4 mol), P-phenylene diacrylic acid 174.4 P (0.8 mol) and 1,4-butanediol 360F (4 moles), stirred while blowing nitrogen gas, and heated from room temperature to 200℃.
After raising the temperature to 200° C., the mixture was heated and reacted for 8 hours. Ggi Iko, diaminodiphenylmethane 39.69 (0,
2 mol) was added thereto, and the imidization reaction and condensation reaction were continued for an additional 3 hours. Excess 1,4-butanediol was distilled off under reduced pressure,
In order to further increase the degree of condensation, heat condensation was carried out at 200° C. for 2 hours under reduced pressure of about 1×1-ip. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.42 meq/FI-1 acid value of 0.05 meq/2, and was solid at room temperature.

For 100 parts of this unsaturated ester imide compound,
45 parts of trismercaptopropyl isocyanurate was blended and melt-mixed to obtain a photocurable resin composition of the present invention. This composition was liquid at 30°C and had a viscosity of 286 voids at the same temperature.

Example 6 54.8 y (0.4 mol) of P-aminobenzoic acid was converted into m-
300 m/g of cresol was dissolved under heat, added to a hot solution containing 64.4 y (0.2 mol) of benzophenone tetracarboxylic dianhydride in 200 rnl of m-Fresol, and heated at 200°C for 5 hours. This heating width is approximately 6.
5rnl of water was distilled off. The pale yellow imide acid having the structure represented by the general formula (3) formed in the reactor contents was cooled and filtered, washed with methanol and water, and then
Dry.

56.0 g (0.1 mol) of this imidic acid, 96.0 g (0.1 mol) of 4-carboxycinnamic acid. Of! (0.5 mol), fumaric acid 46
．． 4p (0,4 mol) and diethylene glycol 42
4Li (4 moles) was charged into a fourth flask equipped with a partial condenser, stirred while blowing nitrogen gas, heated from room temperature to 190°C, and then heat-shrinked for 111 hours. Then, excess ethylene glycol was distilled off under a reduced pressure of 4wnHid, and in order to further increase the degree of condensation, the mixture was heated and condensed at 200° C. for 4 hours under a reduced pressure of 1 ramHf. The unsaturated ester imide compound thus obtained has a hydroxyl value of 0.62 milJ equivalent/g and an acid value of 0.
．． It had an IJ equivalent of 1/y and was solid at room temperature.

45 parts of trismercaptopropyl isocyanurate was blended with 100 parts of this unsaturated esterimide compound, and the mixture was melt-mixed to obtain a photocurable resin composition of the present invention. This composition was liquid at 30° C. and had a viscosity of 350 voids at the same temperature.

Example 7 P-aminobenzoic acid 137y (1 mol) was dissolved in m-cresol 500- while heating, and this was dissolved in m-cresol 500-
1,2,3,4-butanetetracarboxylic acid 11 in rnl
In addition to a hot solution containing 7y-(0,5 mol) at 200 °C
It was heated for 6 hours. Approximately 34 cm of water was distilled out over the heating width. When the contents of the reactor were poured into methanol, a pale yellow imide acid having a structure represented by the general formula (3) was crystallized. The crystals were collected by filtration, thoroughly washed with methanol, and then dried under reduced pressure.

This imidic acid 87.2 f! (0.4 mol), maleic anhydride 49.02 (0.5 mol), adipic acid 14.6
p (0,1 mol) and 1,4-butanediol 360
P (4 moles) was placed in a four-eye flask with a partial condenser, and stirred while blowing nitrogen gas.
After raising the temperature from room temperature to 200°C, the mixture was heated and condensed for 9 hours. Then, under reduced pressure of 4+++ mHp, excess 1.4-
Butanediol was distilled off, and in order to further increase the degree of condensation, the mixture was heated and condensed at 210°C under a reduced pressure of 1wn1lp for 3 hours. □The unsaturated ester imide compound thus obtained has a hydroxyl value of 0.78.
It had a milliequivalent/9, an acid value of 0.15 milliequivalent/V, and was semi-solid at room temperature.

and trismercaptopropyl isocyanurate 25
1 part and 5 parts of 2-hydroxy-2-methylpropiophenone (photosensitizer) were blended and melt-mixed to obtain a photocurable resin composition of the present invention.

This composition was liquid at room temperature and had a viscosity of 140 poise at 30°C.

Example 8 Imidic acid 87.21i' (0,
4 mo/l/)% P-phenylene diacrylic acid 109S'
(0,5 mol), phthalic anhydride 14.8 F (0,1
mol) and 1-4-butanediol 360Si (4 mol) were placed in a four-bottle flask equipped with a partial condenser, stirred while blowing nitrogen gas, heated from room temperature to 210°C, and then heat-condensed for 122 hours. . SoQζ, 4mHf! Excess 1,4-butanediol was distilled off under reduced pressure of 1 mmH! to further increase the degree of condensation.
The mixture was heated and condensed for 2 hours under reduced pressure at 210°C. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.62 mm/V, an acid value of 0.2 mm/IJ, and was solid at room temperature.

45 parts of trismercaptopropyl isocyanurate and 2 parts of 2-hydroxy-2-methylpropiophenone are blended with 100 parts of this unsaturated esterimide compound and melt-mixed to form the photocurable resin composition of the present invention. It became a thing. This composition was liquid at room temperature and had a viscosity of 230 voids at 30°C.

When the three types of curable compositions of Examples 4 to 8 described above were coated on copper foil to a thickness of 100 μm, a beautiful coating film could be easily formed by coating at room temperature. On the other hand, if each composition does not contain trismercaptopropyl isocyanurate, it is impossible to apply it at room temperature, and it must be melted and applied while heating to an appropriate temperature, making the application process troublesome. At the same time, a beautiful coating film could not be obtained and the properties of the coating film could not be said to be good.

In addition, after the above coating, the photocuring treatment was performed in the same manner as in Example 1, and the 10% weight loss temperature change of each photocured film was examined, as shown in Table 3 below. In the table, A indicates the result of this example, and B indicates the result when trismercaptopropyl isocyanurate was removed from the composition of each example for reference.

Table 3 (*) The number of blended parts of benzoyl isopropyl ether is 5
Department.

As can be understood from the above table, the curable composition of the present invention can form a cured film with excellent heat resistance compared to the unsaturated esterimide compound alone without trismercabutopropyl inocyanurate. It can be seen that comparable results are obtained.

Patent applicant: Nitto Electric Industry Co., Ltd.

Claims (4)

[Claims] (1) An unsaturated ester imide compound having an imide bond and a crosslinkable ethylenic double bond in the main chain of the molecule, and a hydroxyl group or carboxyl group at both ends of the molecule, and a trismercaptopropylisocyanuride double bond. A curable resin composition having excellent heat resistance. (2) Claim No. + containing a maleimide compound or triallyl isocyanurate as a curable subcomponent
A curable resin composition with excellent heat resistance according to item 11. (3) The content of tris-mercaptopropyl isocyanurate is 0.3 to 2 equivalents of mercapto groups to the ethylenic double bond contained in the unsaturated ester imide compound (or this and the maleimide compound or triallyl isocyanurate). A curable resin composition having excellent heat resistance according to claim (1) or (2), which has a proportion of (-5H group). (4) Claim No. 1 which is curable with 6 rays of radiation such as ultraviolet rays containing 0 to 20 parts by weight of a sensitizer such as a photosensitizer per 100 parts by weight of the unsaturated esterimide compound. ), (2) or (3), the curable resin composition having excellent heat resistance.