JPH0158221B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention mainly relates to a curable resin composition having good heat resistance, which can be crosslinked and cured by radiation such as ultraviolet rays, and optionally can be crosslinked and cured thermally. 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, and are mainly used as protective materials, insulating materials, solder resists, adhesives, coating materials, etc. in the electrical and electronic fields. It is 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 desired that the material exhibits good adhesion and also satisfies various 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. Certain unsaturated esterimide compounds are cured by radiation such as ultraviolet rays, resulting in improved heat resistance and
It has good insulation properties, moisture resistance, chemical resistance, etc., and also has excellent storage stability when stored in a pre-cured solution state, making it an extremely suitable radiation-curable material. , already found out. However, according to subsequent research by the inventors, the above-mentioned specific unsaturated esterimide compounds are generally solid or semi-solid at room temperature;
When handling without solvent or with a small amount of solvent, heating methods such as melt coating are required.
Furthermore, even if such heating means were used, a beautiful finished surface could not be obtained in some cases. Such problems are
This can usually be avoided by using the necessary amount of organic solvent, but in this case, there is a risk of resource and energy conservation problems due to the use of a large amount of organic solvent. On the other hand, it is common practice to blend monomeric liquid compounds that can be polymerized and crosslinked by radiation or heat into general curable materials to improve handling and workability of the curable materials. As such liquid compounds, diacrylate monomers of ethylene glycol, divinyl compounds such as divinylbenzene, diacryl phthalate, diallylisophthalate, 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 its handling properties as a curable material, it has the disadvantage that its heat resistance decreases during curing, which impairs the excellent heat resistance that is one of the characteristics of unsaturated esterimide compounds. It was hot. In light of the above-mentioned circumstances, this invention has been further investigated 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 during curing. It was completed based on this 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. In this way, the curable resin composition of this invention
Trismercaptopropyl isocyanurate is blended with the unsaturated ester imide compound as described above, and by this, a liquid to semi-solid composition can be obtained at room temperature without using any or almost no organic solvent. Since this composition can be applied at room temperature or by being slightly heated, the workability during use is greatly improved. 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 double bond and the mercapto group (-SH) of trismercaptopropyl isocyanurate is the main one, rather than the secondary reaction of polymerization itself. Although this reaction uses a radical polymerization mechanism like the former, it is hardly affected by the polymerization inhibiting effect of oxygen in the air, and this has the characteristic that the overall curing speed is extremely fast. . Moreover, the product cured in this way shows no decrease in heat resistance due to the isocyanurate ring contained in trismercaptopropyl isocyanurate, and has an excellent property that is almost as good as that of the unsaturated esterimide compound alone. Shows heat resistance,
Furthermore, 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 associated with the improved coating workability, and has excellent general dynamic properties such as insulation properties, moisture resistance, and chemical resistance, and can be stored in a liquid state before use. It also has sufficient storage stability. By the way, conventionally known photosensitive materials include unsaturated oligomers with (meth)acryloyl or allyl groups at the molecular ends, pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-mercaptopropionate), etc. ), ethylene glycol dimethyl captopropionate, 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 not only extremely poor in heat resistance, but also had a very strong odor from the raw material polythiol, making it lacking in industrial utility. On the other hand, the above-mentioned trismercaptopropyl isocyanurate used in this invention has a high boiling point and high vapor pressure, even though it is a type of polythiol, so it is difficult to handle unsaturated Even after being cured with a polyesterimide compound, it has a weak odor and provides an essentially odorless heat-resistant cured product, 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 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 dibasic acid containing an imide group (hereinafter simply referred to as imidic acid), and a dibasic acid having an ethylenic double bond that can be crosslinked with this (hereinafter simply referred to as a crosslinkable dibasic acid). This is a method in which a polybasic acid (referred to as a basic 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 include those with structures represented by the following general formulas (1), (2), and (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:
General formula (4) below; (X is the same as above) 1 mol of tricarboxylic acid anhydride represented by
It can be synthesized by reacting with 1 mole of an aminocarboxylic acid represented by the following general formula (5): H ₂ N--Y--CCOH (5) (Y is the same as above). The reaction is generally carried out in the presence of a suitable organic solvent such as cresol;
Moreover, there is no problem even if the amount of one of the raw materials is slightly larger than the theoretical number of moles mentioned above. Examples of the tricarboxylic acid monoanhydride used here include trimellitic anhydride, 3.4.
4'-Diphenyl ether tricarboxylic acid monoanhydride, ethylene tricarboxylic acid monoanhydride, 2.3.
Examples include 6'-naphthalenetricarboxylic acid monoanhydride. Typical examples of aminocarboxylic acids represented by general formula (5) 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 composed of 2 moles of tricarboxylic acid monoanhydride represented by the above general formula (4) and the following general formulas (6) and (7); H ₂ N- It can be synthesized by reacting with 1 mol of a diamine or diisocyanate represented by Q-NH ₂ ...(6) OCN-Q-NCO ...(7) (Q is the same as above). 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 monoanhydride used here is
The same as above, but the diamines include diaminophenylmethane, diaminodiphenyl ether, m-phenylenediamine, o-phenylenediamine, P-phenylenediamine, 4.
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl, 4,4'-diaminobenzophenone, 2,4-toluenediamine, 2,6-toluenediamine, hexamethylenediamine, ethylenediamine, xylenediamine , diaminopropane, etc. Further, as the diisocyanate, the same organic group (Q) as the above diamine can be used. Furthermore, the imidic acid having the structure represented by the general formula (3) has the following general formula (8); (Z is the same as above) or 1 mol of a tetracarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid and the above general formula (5). It can be synthesized by reacting with 2 moles of aminocarboxylic acid. 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',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Examples include anhydride, 2,2'-bis(3,4-dicarboxyphenyl)propane dianhydride, and 1,2,3,4-butanetetracarboxylic dianhydride. The crosslinkable dibasic acid used in combination with such imide acid has at least one crosslinkable ethylenic double bond in its molecule, and the ethylenic double bond is Dibasic acids with relatively low photosensitivity (hereinafter referred to as group A crosslinking acids) and dibasic acids with high photosensitivity, depending on whether they are easily sensitive to light such as ultraviolet light in the presence of Acid (hereinafter referred to as group b crosslinking acid)
It can be broadly classified into. 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-di-γ-crotonic acid-4,4' [HOOC-CH=CH-CO-Ph-CO ―
Examples include CH=CH—COOH (Ph is a phenyl group). Further, specific examples of group b crosslinking acids include P-phenylene diacrylic acid, m-phenylene diacrylic acid, 4-carboxycinnamic acid, 3-phenylene diacrylic acid,
-Carboxycinnamic acid, cinnamylidenemalonic acid, or derivatives thereof. These crosslinking dibasic 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. May be used. The proportion of such crosslinking dibasic acid used is usually 0 to 95 mol%, preferably 60 to 90 mol% of the total amount with the above-mentioned imide acid.
All you have to do is make it so that However, the optimum proportion used varies somewhat depending on the structure of the imidic acid and the type of crosslinkable dibasic acid. In any case, it is necessary that the cross-linking dibasic acid be used in an appropriate proportion to the imidic acid; if the amount of the dibasic acid used is too small, the curing speed will be slow and it may be impractical. If the amount is too large, the amount of imide acid used will be reduced 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 dibasic acid, but in addition to these acid components, non-crosslinking It may be used in combination with other dibasic acids. Such non-crosslinking acids are used for the purpose of finely adjusting the properties of crosslinking and curing, so if too much is used, heat resistance, curability, and other general properties may be impaired; It is desirable that the amount is within the range of 30 mol% or less in the basic acid component. Specific examples of the non-crosslinking dibasic acid include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, tetrachlorphthalic anhydride, 3,6-endomethylenetetrachlorophthalic acid, tetrachlorophthalic acid,
It includes a wide range of aromatic, aliphatic or alicyclic dibasic acids such as adipic acid, sebacic acid and thiodiglycolic acid, and derivatives thereof. The polyols reacted with the polybasic acid component are
Generally, diols are used, but in some cases, tri- or more polyols may be used in combination with the diols. Specific examples of these include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, cyclohexane diethanol, hydrogenated bisphenol A, 1,4-butanediol, 1.
Examples include diols such as 5-pentanediol and hexamethylene glycol, and triols such as glycerin and tris(hydroxyalkyl)isocyanurate. The condensation reaction between a polybasic acid component and polyols is usually carried out by heating the reaction using an excess of polyols, and then distilling off unreacted polyols under reduced pressure.
This is then carried out by further heating the reaction to achieve a high degree of condensation. In this case, a method may be adopted in which one of the polybasic acid components, imide acid or crosslinking dibasic 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 organic organic compounds such as cresol and N-methyl-2-pyrrolidone are used during the synthesis of imidic acid. It requires a solvent. Therefore,
If you wish to avoid the use of such organic solvents,
The following second and third methods may also be adopted. The second method involves not synthesizing the imide acids represented by the general formulas (1), (2), and (3) in advance.
First, the acid components represented by general formulas (4), (8), etc., which are raw materials for the synthesis of imide acid, the crosslinkable dibasic acid, and if necessary, other non-crosslinkable dibasic acids are mixed into a polyol. In this method, a predetermined polyester is synthesized by reacting with the polyester, and an amino group-containing compound represented by the general formulas (5) and (6) is added thereto 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 can be heated in the presence of an excess of polyol. In order to maintain a molten liquid state, a uniform reaction can be carried out by adding an amino group-containing compound to this. In addition, in the third method, similarly to the second method, the imidic acid is not synthesized in advance, and the acid components represented by general formulas (4), (8), etc., which are the raw materials for the synthesis of the imidic acid, are Then, the amino group-containing compound represented by general formula (5) or (6), the crosslinking dibasic acid, other non-crosslinking dibasic acid if necessary, and polyols are simultaneously added to a reactor. This is a method in which the condensation reaction and imidization reaction are carried out at the same time. Also in this method, the use of organic solvents can be avoided by using polyols in excess. Note that the usage ratio of each raw material in the second and third methods is the same as in the first method. In addition, in the second and third methods, the diisocyanate represented by the 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. This is to become. 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 dibasic acid, and has free at least at both ends of the molecule. having a carboxy group or a hydroxyl group,
It has a hydroxyl value of usually 0.2 to 1.5 milliequivalents/g and an acid value of usually 1.0 milliequivalents/g or less, and is solid or solid at room temperature. If the above hydroxyl value becomes too low,
Even if tris-mercaptopropyl isocyanurate is added to the high-molecular-weight product, it will not have the effect of lowering the viscosity, making it difficult to improve workability during use.On the other hand, if the concentration is too high, it will become a low-molecular-weight product. Properties such as chemical resistance and flexibility are likely to be adversely affected after curing. 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 has the following structural formula; It has a low viscosity of about 53 poise at room temperature (25°C). The proportion of trismercaptopropyl isocyanurate 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 5 parts by weight per 100 parts by weight of the unsaturated esterimide compound.
~70 parts by weight, preferably 20-50 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 curable resin composition of the present invention obtained in this manner is resistant to 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 radiation such as rays, and can also be cured by heating if necessary. In a particularly preferred embodiment of this invention, the resin composition that can be cured by ultraviolet rays contains a sensitizer such as a photosensitizer, an unsaturated esterimide compound, etc.
It can be added in an amount of 0 to 20 parts by weight per 100 parts by weight. 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 above-mentioned double bond is derived from a group b 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 hydride, halogen compounds, and photoreducible dyes. Further, spectral sensitizers such as N-acetyl-4-nitronaphthylamine and 5-nitroacenaphthene can also be used. 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, it is possible to improve the curing function by first curing with ultraviolet rays and then performing a post-heat treatment. Examples of such organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, and the like.
The proportion used may be 5 parts by weight or less per 00 parts by weight of the unsaturated esterimide compound. Next, for a thermosetting resin composition that can be cured by heat treatment, which is one embodiment of the present invention, an organic peroxide is generally used as a thermosetting catalyst as described above, and an organic peroxide is used as a thermosetting catalyst. It is usually added in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the saturated ester imide compound. As described above, the curable resin composition of this invention has
Photosensitizers, organic peroxides, etc. are appropriately blended depending on whether the material is UV curable or heat curable, but in addition to these ingredients, curable By incorporating a maleimide compound or triallylsocyanurate as a subcomponent, the heat resistance during curing can be further improved, or the coating workability can be further improved by lowering the viscosity. Typical examples of the above maleimide compounds include the following general formula; (R ₁ is hydrogen, alkyl group or phenyl group, R ₂
is a monovalent organic group) and the following general formula; (R ₁ is the same as above, R ₃ is a divalent organic group) There is a bismaleimide represented by the following. In the monomaleimide represented by the general formula (9), R ₂ in the formula is preferably an alkyl group, an aryl group, an aracyl group, or a halogen-substituted product thereof, such as N-phenylmaleimide, N-p
-Toluylmaleimide, N-m-toluylmaleimide, N-α-naphthylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-
Octylmaleimide, N-dodecylmaleimide,
Examples include 2-methylethylmaleimide, 2-phenylphenylmaleimide, 2-methylphenylmaleimide, and the like. In the bismaleimide represented by the general formula (10), R ₃ in the formula is preferably an alkylene group, an arylene group, or an aralkylene group, for example,
N・N′-p-phenylerene bismaleimide,
N・N′-m-phenylene bismaleimide, N・
N′-(oxy-p-phenylene) bismaleimide, N・N′-(methylene-di-p-phenylene)
Bismaleimide, N・N′-(methylene di-p
-phenylene)bis[2-methylmaleimide],
N・N′-(methylene-di-p-phenylene)bis[2-phenylmaleimide], N・N′-2.4
-Tolylene bismaleimide, N/N'-2/6-
Tolylene bismaleimide, N/N'-m-xylylene bismaleimide, N/N'-p-xylylene bismaleimide, N/N'-oxypropylene bismaleimide, N/N'-ethylene bis [oxypropylene bis] Maleimide], N/N'-oxydiethylene bismaleimide, N/N'-ethylene bismaleimide, N/N'-ethylenebis[2-methylmaleimide], N/N'-trimethylene bismaleimide, N/N '-tetramethylene bismaleimide, N·N'-hexamethylene bismaleimide, N·N'-hexamethylene bissus [2-methylmaleimide], N·N'-dodecamethylene bismaleimide, and the like. These bismaleimide compounds or triallylisocyanurates are preferably used in an amount of 0 to 40 parts by weight 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 be impaired. I don't like it because I get lost. 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 trismercaptopropylisocyanurate is generally in the above-mentioned equivalent amount, 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 tetrahydrofuran to finely adjust the amount depending on the purpose of use. A small amount of an appropriate organic solvent such as the following may be blended. 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 the present invention, since it is in a liquid or semi-solid state at room temperature, it can be used as it is at room temperature or with slight heating, for example with a bar coater, applicator, etc.
It can be applied to adherends using a spinner, and by irradiating this coating with radiation such as ultraviolet rays, and optionally heat-treating it, it is cured with a beautiful surface appearance and the excellent properties mentioned above. Can form a film. Examples of this invention will be described below. In the following, parts and % refer to parts and % by weight.
shall mean. Example 1 198 g of 4,4'-diaminodiphenylmethane (1.0
mol) and 384 g (2.0 mol) of trimellitic anhydride, and then added N-methyl-2-pyrrolidone.
Add 1000g, stir while blowing nitrogen gas, raise the temperature from room temperature to 150℃, and then heat to 150-160℃
The mixture was heated and reacted for 2 to 3 hours. The reactor contents are
The imide acid having the structure represented by the general formula (2) was precipitated by pouring it into a large amount of ethanol, and after filtering and thoroughly washing with methanol, it was dried under reduced pressure at 100°C. This imidic acid 66.3g (0.15 mol), fumaric acid 98.6g
(0.85 mol) and 310 g (5 mol) of ethylene glycol were placed in a four-necked flask equipped with a partial condenser, stirred well while blowing nitrogen gas, and heated to 190°C from room temperature, followed by heating condensation for 8 hours. I let it happen. At that time, excess ethylene glycol was distilled off under reduced pressure, and in order to further increase the degree of condensation, the mixture was heated at 200° C. for 3 to 4 hours under reduced pressure of about 4 mmHg. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.55 meq/g, an acid value of 0, and was semisolid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
35 parts of benzoin isopropyl ether and 6 parts of benzoin isopropyl ether 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 272 poise at 30°C. Example 2 To 100 parts of the unsaturated ester imide compound obtained in Example 1, 25 parts of trismercaptopropyl isocyanurate, 20 parts of triallyl isocyanurate, and 6 parts of benzoin isopropyl ether
The photocurable resin composition of the present invention was prepared by blending the following parts and melt-mixing them. This composition was liquid at room temperature and had a viscosity of 225 poise at 30°C. Example 3 To 100 parts of the unsaturated ester imide compound obtained in Example 1, 35 parts of trismercaptopropyl isocyanurate, 5 parts of N-N'-(methylene-di-p-phenylene) bismaleimide, and benzoin isopropyl 6 parts of ether was blended and melt-mixed to obtain a photocurable resin composition of the present invention. This composition is liquid at room temperature, and the viscosity at 30℃ is
It was 305 poise. Comparative Example To 100 parts of the unsaturated ester imide compound obtained in Example 1, 40 parts of ethylene glycol diacrylate and 5 parts of benzoin isopropyl ether were blended and melt-mixed to form a photocurable resin composition. did. This composition is liquid at room temperature,
The viscosity at 30°C was 180 poise. Reference Example 5 parts of benzoin isopropyl ether was added to 100 parts of the unsaturated ester imide compound obtained in Example 1, and the mixture was melt-mixed to obtain a photocurable resin composition. This composition was semi-solid at room temperature. Coating workability and film properties when the curable resin compositions of Examples 1 to 3, Comparative Examples, and Reference Examples above were coated on copper foil to a thickness of 100μ, and their respective properties. Input per unit length is 30W/cm,
Using two high pressure mercury lamps with a lamp output of 1KW,
The 10% weight loss temperature of the cured product when it was photocured by irradiation from a position 20 cm away from the coating surface for 5 minutes was investigated, and the results were as shown in Table 1 below.

【table】

[Table] As is clear from the above table, it can be seen that the curable composition of the present invention allows good coating work and 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】

[Table] Example 4 134.4 g (0.7 mol) of trimellitic anhydride, 75.4 g (0.65 mol) of fumaric acid, and ethylene glycol were placed in a four-neck flask equipped with a partial condenser.
Pour 186g (3 moles), stir while blowing nitrogen gas, and raise the temperature from room temperature to 200℃.
The reaction was carried out by heating at ℃ for 6 hours. Next, 69.3 g (0.35 mol) of diaminophenylmethane was added, and the imidization reaction and condensation reaction were continued for an additional 3 hours. Thereafter, excess ethylene glycol was distilled off under reduced pressure, and in order to further increase the degree of condensation, the mixture was heated at 200° C. for 2 hours under reduced pressure of about 4 mmHg. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.62 meq/g, an acid value of 0.03 meq/g, and was solid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
45 parts of benzoin isopropyl ether and 7 parts of benzoin isopropyl ether were blended and melt-mixed to obtain a photocurable resin composition of the present invention. This composition is liquid at room temperature,
The viscosity at 30°C was 115 poise. Example A four-necked flask equipped with a partial condenser was charged with 79.2 g (0.4 mol) of trimellitic anhydride, 174.4 g (0.8 mol) of p-phenylene diacrylic acid, and 360 g (4 mol) of 1,4-butanediol. , stir while blowing nitrogen gas, and heat from room temperature.
After raising the temperature to 200°C, a heating reaction was performed at 200°C for 8 hours. Next, 39.6g of diaminodiphenylmethane
(0.2 mol) was added, and the imidization reaction and condensation reaction were continued for an additional 3 hours. Thereafter, excess 1,4-butanediol was distilled off under reduced pressure, and in order to further increase the degree of condensation, the mixture was heated at 200° C. for 2 hours under reduced pressure of about 1 mmHg. The unsaturated ester imide compound thus obtained has a hydrogen value of 0.42.
It had a milliequivalent/g and an acid value of 0.05 milliequivalent/g, and was solid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
45 parts were 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 poise at the same temperature. Example 6 54.8 g (0.4 mol) of p-aminobenzoic acid was dissolved in 300 ml of m-cresol under heating, and this was dissolved in 200 ml of m-cresol containing 64.4 g (0.2 mol) of benzophenonetetracarboxylic dianhydride. In addition to the hot solution,
It was heated at 200°C for 5 hours. Approximately 6.5 ml of water was distilled out during this heating. The pale yellow imide acid having the structure represented by the general formula (3) which was precipitated in the contents of the reactor was cooled and filtered, washed with methanol and water, and then dried. This imidic acid 56.0g (0.1mol), 4-carboxycinnamic acid 96.0g (0.5mol), fumaric acid 46.4g (0.4mol) and diethylene glycol 424g (4mol)
was charged into a four-neck flask equipped with a partial condenser, stirred while blowing nitrogen gas,
After raising the temperature from room temperature to 190°C, the mixture was heated and condensed for 11 hours. Thereafter, excess ethylene glycol was distilled off under a reduced pressure of 4 mmHg, 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 mmHg. The unsaturated esterimide compound thus obtained has a hydroxyl value of 0.62 milliequivalent//
g, the acid value was 0.1 meq/g, and it was solid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
45 parts were 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 350 poise at the same temperature. Example 7 137 g (1 mol) of p-aminobenzoic acid was dissolved in 500 ml of m-cresol under heating, and this was dissolved in 500 ml of m-cresol containing 117 g (0.5 mol) of 1,2,3,4-butanetetracarboxylic acid. In addition to the hot solution, 200
Heated at ℃ for 6 hours. Approximately 34 ml of water was distilled out during this heating. When the contents of the reactor were poured into methanol, a pale yellow imidic acid having a structure represented by the above general formula (3) was crystallized. The crystals were collected by filtration, thoroughly washed with methanol, and then dried under reduced pressure. 87.2g (0.4mol) of this imidic acid, maleic anhydride
49.0 g (0.5 mol), adipic acid 14.6 g (0.1 mol), and 360 g (4 mol) of 1,4-butanediol were placed in a four-necked flask equipped with a partial condenser, stirred while blowing nitrogen gas, and cooled to room temperature. After raising the temperature from 200°C to 200°C, the mixture was heated and condensed for 9 hours.
Thereafter, excess 1,4-butanediol was distilled off under a reduced pressure of 4 mmHg, and in order to further increase the degree of condensation, the mixture was heated and condensed at 210° C. for 3 hours under a reduced pressure of 1 mmHg. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.78 meq/g, an acid value of 0.15 meq/g, and was semisolid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
25 parts 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 87.2 g (0.4 mol) of imidic acid obtained in Example 7,
109 g (0.5 mol) of p-phenylene diacrylic acid, 14.8 g (0.1 mol) of phthalic anhydride, and 360 g (4 mol) of 1,4-butadiol were placed in a four-necked flask equipped with a partial condenser, and nitrogen gas was added. The mixture was stirred while being blown into the mixture, and the temperature was raised from room temperature to 210°C, followed by heating and condensation for 12 hours. That's 4mm
Excess 1,4-butanediol was distilled off under a reduced pressure of Hg, and in order to further increase condensation, the mixture was heated at 210° C. for 2 hours under a reduced pressure of 1 mmHg. The unsaturated esterimide compound thus obtained had a hydroxyl value of 0.62 meq/g, an acid value of 0.2 meq/g, and was solid at room temperature. For 100 parts of this unsaturated ester imide compound, trismercaptopropyl isocyanurate
45 parts and 2 parts of 2-hydroxy-2-methylpropiophenone were blended and melt-mixed to obtain a photocurable resin composition of the present invention. This composition is
It was liquid at room temperature and had a viscosity of 230 poise at 30°C. When the five 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 trismercaptopropyl isocyanurate is not included in each composition,
Both methods cannot be applied at room temperature and must be melted and applied while being heated to an appropriate temperature, which makes the application process troublesome and does not result in a beautiful coating, although the coating properties are good. Nakatsuta. Further, after the above coating, a photocuring treatment was performed in the same manner as in Example 1, and the 10% weight loss temperature of each photocured film was examined, and the results were as shown in Table 3 below. In addition, in the table, A means the result of this example, and B
For reference, the results are shown when trismercaptopropyl isocyanurate is removed from the composition of each example.

[Table] As can be understood from the above table, the curable composition of the present invention can form a cured film with excellent heat resistance. It can be seen that comparable results are obtained.

Claims (1)

[Claims] 1. The following general formulas (1) to (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) An imide group-containing dibasic acid or its Synthetic raw materials, dibasic acids with crosslinkable ethylenic double bonds, and polyols, which have an imide bond and a crosslinkable ethylenic double bond in the molecular main chain, and which have no molecular double bonds. A product with excellent heat resistance characterized by containing an unsaturated esterimide compound having a hydroxyl group or a carboxyl group at the end and trismercaptopropyl isocyanurate in a proportion of 5 to 70 parts by weight per 100 parts by weight of this compound. Curable resin composition. 2. The curable resin composition with excellent heat resistance according to claim 1, which contains a maleimide compound or triallyl isocyanurate as a curable subcomponent. 3 The content of tris mercaptopropyl isocyanurate is 0.3 to 2 equivalents of mercapto groups (-SH group) 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 with excellent heat resistance according to claim 1 or 2, wherein the composition has a ratio of: 4. Claims 1 and 2 that are curable with radiation such as ultraviolet rays and contain 0 to 20 parts by weight of a sensitizer such as a photosensitizer per 100 parts by weight of the unsaturated esterimide compound. A curable resin composition having excellent heat resistance according to item 1 or 3.