JPWO2005044777A1 - Tetra(meth)acrylate compound, curable composition containing the same, and cured products thereof - Google Patents

Abstract

The (meth)acrylate compound represented by the following general formula (1) and the curable composition containing the same can be used for various applications such as resist inks, paints and molding materials. In addition to the tetra(meth)acrylate compound (B), an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C), a diluting solvent (D), and 2 or more in one molecule. A curable composition containing a compound (E) having a cyclic ether, a curing catalyst (F), etc. is used for producing a solder resist, an etching resist, a plating resist of a printed wiring board, an interlayer insulating layer of a multilayer wiring board, a tape carrier package. It is useful for applications such as permanent masks used in, and resists for color filters. (However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group, and X represents a dicarboxylic acid residue, preferably an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue.)

Description

  The present invention relates to a novel tetra(meth)acrylate compound, a curable composition containing the same, and a cured product thereof, and can be used in various applications such as resist inks, paints and molding materials.

  Further, the present invention relates to a curable composition used for producing a printed wiring board, etc., and more specifically, it has excellent resistance to cracking and electrical insulation due to heat cycles, PCT (pressure cooker test) resistance, and adhesion. The present invention relates to a curable composition that gives a cured product having excellent properties such as solder heat resistance, chemical resistance, and resistance to electroless gold plating, and a cured product thereof.

  In recent years, curable compositions containing (meth)acrylate compounds have been widely used in the fields of aerospace and electronic materials because of their excellent reactivity and processability. In particular, in the production of composite materials used in the aerospace industry field, a large amount of a composition comprising a (meth)acrylate compound, a polymerization initiator, and a fiber reinforcing material such as carbon fiber, glass fiber or aramid fiber is used. However, the (meth)acrylate compound is important for obtaining not only the photocurability and/or thermosetting property of the composition but also the moisture absorption resistance of the cured product and the heat resistance and flexibility under high humidity. It is an ingredient.

  However, a composite material obtained by using a curable composition containing a commercially available (meth)acrylate compound has not been able to satisfy both thermal characteristics and flexibility under high humidity and meets the demand for higher performance. The current situation is that it cannot be done. That is, a composite material obtained by using a curable composition containing a commercially available (meth)acrylate compound has a poor thermal and mechanical long-term reliability due to moisture. Such a long-term reliability problem is not limited to the aerospace industry field, and is not desirable in other fields such as the electronic material field.

  In general, electronic materials such as resist materials for printed wiring boards, especially cured films of curable compositions used as solder resists have excellent electrical insulation and PCT (pressure cooker test) resistance, It is required to have excellent properties such as adhesion, solder heat resistance, chemical resistance, and resistance to electroless gold plating.

  In particular, in recent years, printed wiring boards mounted on automobiles are exposed to high temperatures and low temperatures for a long period of time, so that in addition to the above-mentioned characteristics, excellent crack resistance due to heat cycle is required. became. Such characteristics are not limited to the solder resist on the printed wiring board, and are required in products for other uses such as an interlayer insulating layer such as a build-up multilayer wiring board.

  However, the solder resist formed using a conventional curable composition containing a (meth)acrylate compound cannot satisfy both crack resistance due to heat cycle and the above-mentioned properties.

  To solve the above problems, various (meth)acrylate compounds have been newly developed so far, but in order to sufficiently satisfy the characteristics of hygroscopicity, heat resistance and flexibility under high humidity. The current situation is that has not reached yet. For example, a (meth)acrylate compound obtained by reacting a secondary alcoholic hydroxyl group of a bisphenol type epoxy (meth)acrylate resin with acryloyl chloride can be mentioned (see JP-A-9-124714). However, such a (meth)acrylate compound is still insufficient to satisfy both excellent moisture absorption resistance and heat resistance under high humidity. On the other hand, as a (meth)acrylate compound having low hygroscopicity, a di(meth)acrylate compound obtained by reacting terephthalic acid chloride with hydroxybutyl (meth)acrylate has been developed (Japanese Patent Laid-Open No. 2003-2919). reference). However, since this (meth)acrylate compound has two unsaturated groups in one molecule, it is poor in photocurability and/or thermosetting property, and as a result, it is inferior in heat resistance under high humidity. There's a problem. On the other hand, examples of the (meth)acrylate compound having excellent photocurability and/or thermosetting property include a hexa(meth)acrylate compound obtained by reacting terephthalic acid chloride with pentaerythritol tri(meth)acrylate ( (See JP-A-62-52547). However, since this (meth)acrylate compound has six unsaturated groups in one molecule, it is excellent in photocurability and/or thermosetting property, but since it becomes highly crosslinked by curing, a hard and brittle cured product is obtained. Form. Therefore, since the cured product lacks flexibility, it may be destroyed during aging under high humidity.

  Therefore, an object of the present invention is to provide a novel tetra() which is excellent in photocurability and/or thermosetting property, and which is also excellent in moisture absorption resistance and heat resistance and flexibility under high humidity. It is intended to provide a (meth)acrylate compound, a curable composition containing the same, and a cured product thereof.

  Another object of the present invention is excellent in photocurability and/or thermosetting property, and also excellent in crack resistance due to heat cycle, electrical insulation, PCT (pressure cooker test) resistance, adhesion, and solder heat resistance. To provide a curable composition and a cured product thereof which give a cured product sufficiently satisfying various properties such as resistance, chemical resistance and resistance to electroless gold plating.

（但し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は水素原子又はメチル基を表わし、Ｘはジカルボン酸残基を表わす。）To achieve the above object, the present invention provides a tetra(meth)acrylate compound represented by the following general formula (1).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group, and X represents a dicarboxylic acid residue.)

  In addition, in this specification, (meth)acrylate is a general term for acrylate and methacrylate, acrylic acid or methacrylic acid is similarly expressed as (meth)acrylic acid, and an acryloyl group or a methacryloyl group is a (meth)acryloyl group. Described as a group.

According to a preferred embodiment, in the general formula (1), the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue. When the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue, preferably the dicarboxylic acid residue X is any aromatic dicarboxylic acid residue represented by the following formulas (B1) to (B7). , And more preferably an aromatic dicarboxylic acid residue represented by the following formula (B3).

  Furthermore, according to the present invention, a cured product of the tetra(meth)acrylate compound is provided.

  The tetra(meth)acrylate compound of the present invention has four unsaturated groups in one molecule, and a pair of units each having a (meth)acryloyl group at a bifurcated end are thermally stable esters. Since it has a structure in which alkylene or polymethylene or an aromatic ring is linked through a bond or an ester bond, it is excellent in photocurability and/or thermosetting property, and the cured product thereof has high moisture absorption resistance and high Has excellent heat resistance and flexibility under humidity.

  According to another aspect of the present invention, there is provided a curable composition comprising the tetra(meth)acrylate compound represented by the general formula (1). According to a preferred embodiment, a tetra(meth)acrylate compound in which the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue in the general formula (1) is used. When the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue, the dicarboxylic acid residue X is preferably any aromatic dicarboxylic acid residue represented by the formulas (B1) to (B7). , And more preferably an aromatic dicarboxylic acid residue of the formula (B3).

  According to a further preferred aspect of the curable composition of the present invention, other radically polymerizable monomers and/or polymerization initiators are contained together with the tetra(meth)acrylate compound as described above, or a fiber reinforcing material is further added. contains.

  According to still another aspect of the present invention, there is provided a cured product obtained by using the curable composition. According to a preferred embodiment, the cured product contains a fiber reinforcing material such as glass fiber, carbon fiber or aramid fiber.

  Since the curable composition contains the tetra(meth)acrylate compound having the above-described structure, the curable composition is excellent in photocurability and/or thermosetting property, and the cured product is resistant to moisture absorption and high humidity. Excellent heat resistance and flexibility.

  According to another aspect of the present invention, (A) a carboxyl group-containing compound, (B) a tetra(meth)acrylate compound represented by the general formula (1), (C) a polymerization initiator, and (D) a diluting solvent. A curable composition comprising: According to a preferred embodiment, a tetra(meth)acrylate compound in which the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue in the general formula (1) is used. When the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue, the dicarboxylic acid residue X is preferably any aromatic dicarboxylic acid residue represented by the formulas (B1) to (B7). , And more preferably an aromatic dicarboxylic acid residue of the formula (B3).

  According to a further preferred aspect of the curable composition of the present invention, in addition to the above-mentioned components, (E) a compound having two or more cyclic ethers in one molecule, or (F) curing A catalyst, or (G) another radically polymerizable monomer is further contained.

  According to still another aspect of the present invention, a cured product obtained by using the curable composition is provided.

  The curable composition contains an alkali-soluble (A) carboxyl group-containing compound, (C) a polymerization initiator, (D) a diluting solvent, and (B) a tetra(meth)acrylate compound having the above-described structure. Therefore, it is alkali-developable, and is excellent in photocurability and/or thermosetting property, and the cured product thereof is excellent in crack resistance due to heat cycle, and also has electrical insulating property, PCT resistance, adhesiveness, and solderability. It has excellent properties such as heat resistance, chemical resistance, and resistance to electroless gold plating. Further, in the case of a curable composition containing (E) a compound having two or more cyclic ethers in one molecule as a thermosetting component in addition to the above-mentioned components, electrical insulation is obtained by heat curing after exposure and development. Properties, PCT resistance, adhesion, solder heat resistance, chemical resistance, resistance to electroless gold plating, etc. can be further improved, and the curing start temperature can be lowered by containing (F) a curing catalyst. Also, the thermosetting reaction can be accelerated. Alternatively, in the case of a curable composition further containing (G) another radically polymerizable monomer, photocurability is further improved.

3 is a graph showing an infrared absorption spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 1.

3 is a graph showing a nuclear magnetic resonance spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 1.

1 is a graph showing a chromatogram of a tetra(meth)acrylate compound obtained in Synthesis Example 1 by high performance liquid chromatography.

5 is a graph showing an infrared absorption spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 2.

3 is a graph showing a nuclear magnetic resonance spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 2.

3 is a graph showing a chromatogram of a tetra(meth)acrylate compound obtained in Synthesis Example 2 by high performance liquid chromatography.

It is a graph for explaining a method of obtaining a heat resistant temperature from a TG curve.

5 is a graph showing a chromatogram of the oil obtained in Synthesis Example 3 by high performance liquid chromatography.

5 is a graph showing an infrared absorption spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 3.

5 is a graph showing a nuclear magnetic resonance spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 3.

5 is a graph showing a chromatogram of a tetra(meth)acrylate compound obtained in Synthesis Example 3 by high performance liquid chromatography.

7 is a graph showing a chromatogram of the oil obtained in Synthesis Example 4 by high performance liquid chromatography.

9 is a graph showing an infrared absorption spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 4.

9 is a graph showing a nuclear magnetic resonance spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 4.

5 is a graph showing a chromatogram of the obtained tetra(meth)acrylate compound by high performance liquid chromatography.

9 is a graph showing an infrared absorption spectrum of the liquid obtained in Synthesis Example 4.

9 is a graph showing a nuclear magnetic resonance spectrum of the liquid obtained in Synthesis Example 4.

7 is a graph showing a chromatogram of the liquid obtained in Synthesis Example 4 by high performance liquid chromatography.

9 is a graph showing a chromatogram of the oil obtained in Synthesis Example 5 by high performance liquid chromatography.

9 is a graph showing an infrared absorption spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 5.

9 is a graph showing a nuclear magnetic resonance spectrum of the tetra(meth)acrylate compound obtained in Synthesis Example 5.

7 is a graph showing a chromatogram of a tetra(meth)acrylate compound obtained in Synthesis Example 5 by high performance liquid chromatography.

7 is a graph showing a nuclear magnetic resonance spectrum of a mixture of a tetra(meth)acrylate compound obtained in Synthesis Example 6 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

9 is a graph showing a chromatogram obtained by high performance liquid chromatography of a mixture of the tetra(meth)acrylate compound obtained in Synthesis Example 6 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

9 is a graph showing an infrared absorption spectrum of a mixture of a tetra(meth)acrylate compound obtained in Synthesis Example 6 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

3 is a graph showing a nuclear magnetic resonance spectrum of 3-acryloyloxy-2-hydroxypropyl methacrylate.

It is a graph which shows the chromatogram by high performance liquid chromatography of 3-acryloyloxy-2- hydroxypropyl methacrylate.

It is a graph which shows the nuclear magnetic resonance spectrum of the monocarboxylic acid of a structure shown by a formula (3) mentioned below.

9 is a graph showing a nuclear magnetic resonance spectrum of a mixture of a tetra(meth)acrylate compound obtained in Synthesis Example 7 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

9 is a graph showing a nuclear magnetic resonance spectrum of a mixture of the tetra(meth)acrylate compound obtained in Synthesis Example 8 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

9 is a graph showing a chromatogram obtained by gel permeation chromatography of a mixture of the tetra(meth)acrylate compound obtained in Synthesis Example 8 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

9 is a graph showing an infrared absorption spectrum of a mixture of a tetra(meth)acrylate compound obtained in Synthesis Example 8 and 3-acryloyloxy-2-hydroxypropyl methacrylate.

1 is a graph showing a chromatogram of 3-acryloyloxy-2-hydroxypropyl methacrylate by gel permeation chromatography.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly studying in order to solve the said subject, this inventor showed that the tetra(meth)acrylate represented by the said General formula (1) is excellent in photocurability and/or thermosetting property, and its It was found that the cured product has excellent moisture absorption resistance, heat resistance under high humidity, and flexibility.

  In addition, the present inventor has found that a curable composition containing a tetra(meth)acrylate compound represented by the general formula (1), preferably further radical-polymerizable monomer and/or polymerization initiator or further fiber reinforced. A curable composition containing a material gives a cured product which exhibits excellent photocurability and/or thermosetting property, and also has excellent moisture absorption resistance and excellent heat resistance and flexibility under high humidity. I found that. That is, the tetra(meth)acrylate compound represented by the general formula (1) used in the curable composition of the present invention has a thermally stable ester bond and has four unsaturated groups in one molecule. Since it has a group, it is excellent in photocurability and/or thermosetting property, and is also excellent in moisture absorption resistance. Moreover, since it has an appropriate number of unsaturated groups of 4 in one molecule, it is difficult to form a hard and brittle cured film, and a cured product having excellent toughness can be obtained. Therefore, a curable composition containing this tetra(meth)acrylate compound and other radically polymerizable monomers, a polymerization initiator, a fiber reinforcing material, etc. exhibits excellent photocurability and/or thermosetting property. And a cured product having excellent moisture absorption resistance and excellent heat resistance and flexibility under high humidity.

  Further, the present inventor contains the tetra(meth)acrylate compound (B) represented by the general formula (1) together with the carboxyl group-containing compound (A), the polymerization initiator (C), the diluting solvent (D) and the like. The curable composition exhibits excellent photocurability and/or thermosetting property, and the cured product has excellent crack resistance, and also has the above-mentioned electrical insulation, PCT resistance, adhesion, solder heat resistance, It has been found that it gives a cured product having excellent properties such as chemical resistance and resistance to electroless gold plating.

  That is, as the curable component, the tetra(meth)acrylate compound (B) which is excellent in photocurability and/or thermosetting property as described above, and is excellent in water resistance and gives a cured product having excellent toughness. A compound containing an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C) and a diluting solvent (D), and preferably having two or more cyclic ethers in one molecule (E). ), or a curing catalyst (F), or a further radical-polymerizable monomer (G), which is alkali-developable and has excellent photo-curability and/or heat-curability. The cured product is provided with the adhesion, low hygroscopicity, flexibility and heat resistance necessary for obtaining the above-mentioned various properties, by the tetra(meth)acrylate compound (B).

  Below, the tetra(meth)acrylate compound of this invention, the curable composition containing it, and those cured products are demonstrated in detail.

（但し、Ｒ^１、Ｒ^２は水素原子又はメチル基を表わす。）First, the tetra(meth)acrylate compound of the present invention can be obtained by various methods. For example, esterification of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate represented by the following general formula (2) with dicarboxylic acid chloride or dicarboxylic acid or its anhydride or dicarboxylic acid ester may be used. Among these, preferred methods include dehydrochlorination reaction of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate with aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride, and 3-(meth)acryloyloxy-2. -Esterification by a dehydration condensation reaction between hydroxypropyl (meth)acrylate and an aliphatic dicarboxylic acid.

(However, R ¹ and R ² represent a hydrogen atom or a methyl group.)

  The 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate can be obtained by reacting (meth)acrylic acid with glycidyl(meth)acrylate, and (meth)acrylic acid and/or its esters It can also be obtained by a reaction of glycerin with glycerin or a reaction of (meth)acrylic acid with glycidol.

  Examples of the aliphatic dicarboxylic acid chloride include aliphatic saturated dicarboxylic acid halides such as succinic acid chloride, glutaric acid chloride, adipic acid chloride, suberic acid chloride, azelaic acid chloride and sebacic acid chloride, and fumaric acid chloride. Examples thereof include unsaturated dicarboxylic acid halides.

  Further, as the aliphatic dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other saturated aliphatic dicarboxylic acids, maleic acid, fumaric acid. Examples thereof include aliphatic unsaturated dicarboxylic acids such as acids, and examples of the aliphatic dicarboxylic acid anhydrides include succinic anhydride, anhydrides of saturated aliphatic dicarboxylic acids such as glutaric anhydride, and unsaturated aliphatic acids such as maleic anhydride. An anhydride of dicarboxylic acid and the like can be mentioned.

  Further, as the aliphatic dicarboxylic acid ester, for example, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl suberate, dimethyl sebacate, saturated aliphatic dicarboxylic acid ester, dimethyl maleate, etc. An aliphatic unsaturated dicarboxylic acid ester etc. are mentioned.

  Examples of the aromatic dicarboxylic acid chloride include o-phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride and the like.

  Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7. -Naphthalenedicarboxylic acid and the like, and aromatic dicarboxylic acid anhydrides include phthalic acid anhydride and the like.

  Furthermore, examples of the aromatic dicarboxylic acid ester include dimethyl terephthalate and 2,6-naphthalenedicarboxylic acid dimethyl ester.

  Among these aromatic dicarboxylic acid chlorides, aromatic dicarboxylic acids or anhydrides, and aromatic dicarboxylic acid esters, from the viewpoint of reaction yield, availability, etc., aromatic dicarboxylic acid chlorides, particularly terephthalic acid chloride and naphthalenedicarboxylic acid. Acid chloride is preferred.

  The esterification reaction of an aliphatic dicarboxylic acid chloride or an aromatic dicarboxylic acid chloride with 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate is carried out using 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate. Aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride may be placed in a reaction vessel before carrying out, or 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate may be placed in a reaction vessel in advance. In the above, the aliphatic dicarboxylic acid chloride or the aromatic dicarboxylic acid chloride may be added dropwise, or conversely, the aliphatic dicarboxylic acid chloride or the aromatic dicarboxylic acid chloride is placed in the reaction vessel in advance, and 3-( It may be carried out by adding (meth)acryloyloxy-2-hydroxypropyl(meth)acrylate.

  The blending ratio (feeding ratio) of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate and aliphatic dicarboxylic acid chloride is usually 3-(meth)acryloyloxy-2-hydroxypropyl(meth) in molar ratio. Acrylate/aliphatic dicarboxylic acid chloride=4/3 or more is preferable, while the blending ratio (feeding ratio) with the aromatic dicarboxylic acid chloride is usually 3-(meth)acryloyloxy-2-hydroxy. It is desirable that propyl (meth)acrylate/aromatic dicarboxylic acid chloride=4/3 or more, more preferably 2/1 or more. When the proportion of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate used is small, products other than the desired tetra(meth)acrylate such as di(meth)acrylate are likely to be produced and the yield is increased. descend. On the other hand, if the proportion of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate is too high, the polymerization reaction of the unsaturated group is likely to occur and the polymer may be polymerized, which is not preferable. Further, if the proportion of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate is too high, unreacted 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate remains, so economically. Not preferable. Therefore, the ratio of 3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate to aliphatic dicarboxylic acid chloride is 3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate/aliphatic dicarboxylic acid in a molar ratio. Acid chloride=4/3 to 3/1 is preferred, while the ratio with the aromatic dicarboxylic acid chloride is 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate/aromatic dicarboxylic acid in a molar ratio. Acid chloride=4/3 to 3/1, more preferably 2/1 to 3/1. The above mixing ratio is the same when an aliphatic dicarboxylic acid or its anhydride or an aliphatic dicarboxylic acid ester, or an aromatic dicarboxylic acid or its anhydride or an aromatic dicarboxylic acid ester is used.

  The reaction temperature in the esterification reaction of 3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate with an aliphatic dicarboxylic acid chloride is -70 to 150°C, preferably -30 to 120°C, under reduced pressure, The reaction can be carried out under either normal pressure or increased pressure. On the other hand, the reaction temperature in the esterification reaction of 3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate with aromatic dicarboxylic acid chloride is 0 to 150°C, preferably room temperature to 120°C, under reduced pressure, The reaction can be carried out under either normal pressure or increased pressure.

  The esterification reaction is preferably performed in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic hydrocarbons such as n-heptane, cyclohexane and n-hexane, formamide, N, Nitrogen compounds such as N-dimethylformamide are preferably used. These solvents may be used alone or in admixture of two or more. The amount of the solvent used is not particularly limited, but with respect to a total of 100 parts by mass of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate and aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride. Therefore, the range of 50 to 1000 parts by mass is preferable. The reaction temperature and the amount of the solvent used are the same when an aliphatic dicarboxylic acid or its anhydride or an aliphatic dicarboxylic acid ester, or an aromatic dicarboxylic acid or its anhydride or an aromatic dicarboxylic acid ester is used. .

  The esterification reaction is preferably carried out in the presence of a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, 4-methoxyphenol, 4-tertiarybutylcatechol and the like are preferably used. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor used is usually in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate. The amount of the polymerization inhibitor used is the same when an aliphatic dicarboxylic acid or its anhydride or an aliphatic dicarboxylic acid ester, or an aromatic dicarboxylic acid or its anhydride or an aromatic dicarboxylic acid ester is used.

  Furthermore, in order to capture hydrogen chloride generated during esterification, tertiary amines such as trimethylamine, triethylamine, and 4-dimethylaminopyridine are appropriately used. These tertiary amines can capture hydrogen chloride by forming a quaternary ammonium salt with hydrogen chloride. These tertiary amines can be used alone or in admixture of two or more.

  Incidentally, when aromatic dicarboxylic acid chloride, aromatic dicarboxylic acid or anhydride thereof, and aromatic dicarboxylic acid ester are used, after completion of the esterification reaction, a basic salt of amines such as triethylamine is dissolved in water, and then acetic acid is added. An extraction solvent such as ethyl or methylene chloride is added to extract the reaction mixture containing the tetra(meth)acrylate compound of the present invention. Further, in order to remove the amine remaining in the reaction mixture, it is preferable to wash the reaction mixture with an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution or the like. Further, in order to remove the aromatic dicarboxylic acid chloride remaining in the reaction mixture, it is preferable to wash the reaction mixture with an aqueous sodium hydrogen carbonate solution or the like.

  On the other hand, an aliphatic dicarboxylic acid or its anhydride or an aliphatic dicarboxylic acid ester, or an aromatic dicarboxylic acid or its anhydride or an aromatic dicarboxylic acid ester, and 3-(meth)acryloyloxy-2-hydroxypropyl (meth)acrylate The esterification reaction is usually carried out with aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic hydrocarbons such as n-heptane, cyclohexane and n-hexane. Hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol using an esterification catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or cation exchange resin in an organic solvent. , Pyrogallol, phenothiazine, 4-methoxyphenol, 4-tert-butylcatechol and the like in the presence of a polymerization inhibitor.

  The above esterification reaction is carried out by using aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic hydrocarbons such as n-heptane, cyclohexane and n-hexane, and formamide. , N,N-dimethylformamide and other nitrogen compounds in an organic solvent, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and other dehydrating condensing agents, trimethylamine, triethylamine, 4-dimethylamino Hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, 4-methoxyphenol, 4-tertiary using tertiary amines such as pyridine and 1-hydroxy-1-H-benzotriazole hydrate. It can also be carried out in the presence of a polymerization inhibitor such as butylcatechol.

  The tetra(meth)acrylate compound of the present invention comprises 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate represented by the general formula (2) as a reactive diluent and for imparting flexibility. Can be mixed. The mixing amount is sufficient if it is 70 parts by mass or less, preferably 50 parts by mass or less, relative to 100 parts by mass of the tetra(meth)acrylate compound. When the mixing amount of the di(meth)acrylate compound exceeds 70 parts by mass, the heat resistance of the tetra(meth)acrylate compound may be deteriorated, which is not preferable.

  The tetra(meth)acrylate compound of the present invention rapidly radically polymerizes by irradiation with active energy rays and/or heating in the presence of a polymerization initiator (photoradical polymerization initiator, thermal radical polymerization initiator), or simply by heating. It can also be cured by irradiation with X-rays or electron beams.

  Further, the tetra(meth)acrylate compound of the present invention is useful as a resin matrix of a composite material (fiber reinforced plastic). Therefore, the tetra(meth)acrylate compound of the present invention is excellent in photocurability and/or heat curability as described above, and the cured product thereof has hygroscopicity resistance and heat resistance and flexibility under high humidity. It is also extremely useful as a composite material (fiber reinforced plastic), especially in the aerospace industry due to its excellent properties, but it is also used as a curable component of various resist materials for printed wiring boards and paints. be able to.

  First, a curable composition containing the tetra(meth)acrylate compound represented by the general formula (1), particularly, a curable composition further containing another radically polymerizable monomer and/or a polymerization initiator or a fiber reinforcing material. The composition will be described.

  Examples of the radical-polymerizable monomer include styrene derivatives such as styrene and divinylbenzene; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-(meth)acryloyloxy-2-hydroxypropyl (meth ) Hydroxyl group-containing acrylates such as acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate; water-soluble acrylates such as polyethylene glycol diacrylate, polypropylene glycol diacrylate; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, diester Polyfunctional polyester acrylates of polyhydric alcohols such as pentaerythritol hexaacrylate; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A, or ethylene oxide adducts and/or propylene oxide of polyhydric phenols such as bisphenol A and biphenol. Acrylates; polyfunctional or monofunctional polyurethane acrylates which are isocyanate-modified products of the above-mentioned hydroxyl group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or (meth)acrylic acid adduct of phenol novolac epoxy resin Certain epoxy acrylates, and methacrylates corresponding to the above acrylates, or further di(meth)acrylate compounds described in JP-A-2003-2919, tetra(meth)acrylate compounds described in JP-A-9-124714, and Examples thereof include hexa(meth)acrylate compounds described in JP-A-62-52547, and these can be used alone or in combination of two or more kinds. The purpose of using these radically polymerizable monomers is to improve the photocurability and/or thermosetting property of the composition. The radical-polymerizable monomer that is liquid at room temperature serves not only to increase the photocurability and/or thermosetting property of the composition, but also to adjust the composition to have a viscosity suitable for various coating methods. The blending amount of these radically polymerizable monomers can be set to an arbitrary ratio depending on the purpose of use and desired physical properties, but is usually preferably 200 parts by mass or less based on 100 parts by mass of the tetra(meth)acrylate.

  The tetra(meth)acrylate compound used in the present invention can be cured by simply heating and can be cured by irradiation with X-rays or electron beams, but a polymerization initiator (photoradical polymerization initiator, thermal radical polymerization initiation It is preferable to use such a polymerization initiator because radical polymerization is rapidly performed by irradiation with active energy rays and/or heating in the presence of an agent.

  As the polymerization initiator, a photo radical polymerization initiator or a thermal radical polymerization initiator as described below can be preferably used, and the compounding amount thereof is 100 parts by mass of the tetra(meth)acrylate compound (the radical polymerizable monomer. When it is used, the amount is preferably 30 parts by mass or less with respect to the total amount of 100 parts by mass). For example, in the case of a photoradical polymerization initiator, the ratio is 0.1 to 30 parts by mass, In this case, the proportion of 0.1 to 10 parts by mass is preferable.

  Examples of the fiber reinforcement include glass fiber, carbon fiber, and aramid fiber. These fibers can be used alone or as a mixture of two or more kinds. The proportion of this fiber reinforcement in the composition is preferably 10 to 80% by volume, more preferably 50 to 70% by volume.

  In addition, the curable composition of the present invention includes the 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate, an aliphatic dicarboxylic acid chloride or an aliphatic dicarboxylic acid or an anhydride thereof, or an aliphatic dicarboxylic acid. An unreacted monomer at the time of esterification reaction with an ester and a by-product such as a produced di(meth)acrylate compound or a polymer may be contained.

  If necessary, the curable composition of the present invention may further contain a solvent as described below, either alone or as a mixture of two or more kinds. The purpose of using the solvent is to dissolve the tetra(meth)acrylate compound, the radically polymerizable monomer, the polymerization initiator and the like, and to adjust the composition to have a viscosity suitable for the coating method. The blending amount of the solvent can be any amount depending on the coating method.

  The curable composition of the present invention may contain an inorganic thickener as described below to the extent that the properties of the cured product are not deteriorated. The compounding amount of the inorganic thickener is sufficient in a usual quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10.0, relative to 100 parts by mass of the tetra(meth)acrylate compound. It is a ratio of parts by mass.

  The curable composition of the present invention will be further described, if necessary, for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion, hardness, and heat resistance under high humidity. These inorganic fillers and organic fillers may be used alone or in combination of two or more. The amount of the filler to be blended is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the tetra(meth)acrylate compound.

  The curable composition of the present invention further comprises, if necessary, known and commonly used additives such as a colorant, a thermal polymerization inhibitor, a defoaming agent and/or a leveling agent, and a silane coupling agent described below. Can be blended. Further, the curable composition of the present invention may contain a flame retardant such as a halogen-based flame retardant, a phosphorus-based flame retardant, and an antimony-based flame retardant for the purpose of obtaining flame retardancy. The blending amount of the flame retardant is usually 1 to 200 parts by mass, and preferably 5 to 50 parts by mass with respect to 100 parts by mass of the tetra(meth)acrylate compound. When the blending amount of the flame retardant is within the above range, the flame retardancy, moisture absorption resistance, and heat resistance and flexibility under high humidity are highly balanced and suitable.

  The tetra(meth)acrylate compound according to the present invention is extremely useful as a resin matrix of a composite material (fiber reinforced plastic), particularly a composite material used in the field of aerospace industry. This type of composite material is generally obtained by impregnating a fiber reinforcing material, for example, a carbon fiber, a glass fiber, a fiber reinforcing material composed of fibers such as aramid fiber (for example, Kevlar fiber) with a liquid curable composition, and then Obtained by curing. The fiber reinforcement used here can take various forms, for example in the form of layered fibers, two-dimensional sheets or three-dimensional or multidimensional fabrics.

  In addition, a curable composition containing other radically polymerizable monomers, a polymerization initiator and a fiber reinforcement together with the tetra(meth)acrylate compound is loaded into the mold, or the fiber reinforcement is put in the mold in advance. After that, the curable composition of the present invention containing no fiber reinforcement is injected into the mold, and then the mold filled with the composition is heated and cured to obtain a fiber reinforced plastic. You can Alternatively, a fiber-reinforced plastic can be obtained by curing the composition filled in the mold by irradiation with active energy rays. In this case, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is suitable as a light source for irradiating active energy rays. In addition, laser beams, X-rays, electron beams and the like can be used as active energy rays.

  Next, the curable composition of the present invention useful as various resist materials for printed wiring boards, interlayer insulating layers of multilayer printed wiring boards, and the like will be described. This composition contains, in addition to the above-mentioned tetra(meth)acrylate compound (B), an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C), and a diluting solvent (D). Further contains a compound (E) or a curing catalyst (F) having two or more cyclic ethers in one molecule as a thermosetting component, and further contains another radically polymerizable monomer (G) as required. .

  First, the carboxyl group-containing compound (A) used in the curable composition is a compound having at least one, and preferably two or more carboxyl groups in one molecule. Specifically, both a carboxyl group-containing photosensitive resin which itself has an ethylenically unsaturated double bond and a carboxyl group-containing resin which does not have an ethylenically unsaturated double bond can be used. Although not limited to these, resins (both oligomers and polymers) listed below can be preferably used.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond,
(2) A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond,
(3) Secondary compound produced by reacting an unsaturated carboxylic acid (a) with a copolymer of a compound (c) having an epoxy group and an unsaturated double bond and a compound (b) having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with the hydroxyl group of
(4) A copolymer of an acid anhydride (e) having an unsaturated double bond and a compound (b) having an unsaturated double bond is reacted with a compound (f) having a hydroxyl group and an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by
(5) Esterification reaction (total esterification or partial esterification, between the epoxy group of the polyfunctional epoxy compound (g) having at least two epoxy groups in one molecule and the carboxyl group of the unsaturated monocarboxylic acid (h), Preferably total esterification), and a carboxyl group-containing photosensitive resin obtained by further reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d),
(6) Organic compound having one carboxyl group in one molecule and no ethylenically unsaturated bond in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth)acrylate A carboxyl group-containing resin obtained by reacting an acid (i) and reacting a secondary hydroxyl group formed with a saturated or unsaturated polybasic acid anhydride (d);
(7) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer (j) with a saturated or unsaturated polybasic acid anhydride (d),
(8) A compound (c) having an epoxy group and an unsaturated double bond is further added to a carboxyl group-containing resin obtained by reacting the hydroxyl group-containing polymer (j) with a saturated or unsaturated polybasic acid anhydride (d). Carboxyl group-containing photosensitive resin obtained by reaction,
(9) React with a polyfunctional epoxy compound (g) having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid (h), at least two hydroxyl groups in one molecule, and an epoxy group Carboxyl group-containing photosensitivity obtained by reacting a reaction product (I) with a compound (k) having one other reactive group other than a hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d) resin,
(10) Unsaturated group-containing polycarboxylic acid urethane consisting of a reaction product of the reaction product (I), a saturated or unsaturated polybasic acid anhydride (d), and an unsaturated group-containing monoisocyanate (m) resin,
(11) The unsaturated monocarboxylic acid (h) is reacted with the polyfunctional oxetane compound (n) having at least two oxetane rings in one molecule, and the primary hydroxyl group in the obtained modified oxetane resin is saturated or A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated polybasic acid anhydride (d),
(12) Obtained by introducing an unsaturated double bond into a reaction product of a bisepoxy compound (p) and a dicarboxylic acid (q), and subsequently reacting with a saturated or unsaturated polybasic acid anhydride (d). Carboxyl group-containing resin,
(13) Obtained by introducing an unsaturated double bond into a reaction product of a bisepoxy compound (p) and a bisphenol (r) and subsequently reacting with a saturated or unsaturated polybasic acid anhydride (d). The unsaturated monocarboxylic acid (h) is reacted with the carboxyl group-containing resin and (14) the reaction product of the novolac type phenol resin (s) and the alkylene oxide (t), and the resulting reaction product is saturated or unsaturated. A carboxyl group-containing photosensitive resin obtained by reacting a saturated polybasic acid anhydride (d).

  The carboxyl group-containing resin (1) has an unsaturated carboxylic acid (a) such as (meth)acrylic acid and an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth)acrylate and isobutylene. Which is a copolymer of the compound (b), and the carboxyl group-containing photosensitive resin (2) is a copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond. A part of the carboxyl groups of is reacted with a compound having an ethylenically unsaturated group such as a vinyl group, an allyl group or a (meth)acryloyl group and a reactive group such as an epoxy group or an acid chloride, for example, glycidyl (meth)acrylate. , A resin in which an unsaturated double bond of the compound is introduced into a side chain. A part of the carboxyl groups of the unsaturated carboxylic acid (a), which is one of the monomer components of the copolymer, remains unreacted, so that the obtained carboxyl group-containing photosensitive resin is soluble in an alkaline aqueous solution. Is.

  The carboxyl group-containing photosensitive resin of (3) above includes a compound (c) having an epoxy group and an unsaturated double bond in the molecule, such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and the like. The epoxy group of the copolymer of the compound (b) having an unsaturated double bond is reacted with the carboxyl group of the unsaturated carboxylic acid (a), and the unsaturated double bond of the unsaturated carboxylic acid is used as a side chain. At the same time as the introduction, the secondary hydroxyl group generated by the above addition reaction is subjected to an esterification reaction with a polybasic acid anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. It is a resin having a group introduced.

  The carboxyl group-containing photosensitive resin (4) is an acid anhydride (e) having an unsaturated double bond, such as maleic anhydride or itaconic anhydride, and a compound (b) having the unsaturated double bond. A compound (f) having a hydroxyl group and an unsaturated double bond in a part of the acid anhydride group of the copolymer of, for example, hydroxyalkyl (meth)acrylates, a monomer obtained by reacting (meth)acrylate with caprolactone, ( It is a resin in which a hydroxyl group such as a macromonomer obtained by reacting a (meth)acrylate with a polycaprolactone oligomer is reacted to form a half ester, and an unsaturated double bond of the compound (f) is introduced into a side chain.

  The carboxyl group-containing photosensitive resin (5) is a known and commonly used epoxy such as bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolak type, biphenol type, bixylenol type, N-glycidyl type. The epoxy group of the compound (g) is reacted with the carboxyl group of the unsaturated monocarboxylic acid (h) such as (meth)acrylic acid to generate, for example, an epoxy acrylate, and the secondary hydroxyl group generated by the addition reaction. It is a resin in which a carboxyl group is introduced into the side chain by esterifying the polybasic acid anhydride (d).

  The carboxyl group-containing resin (6) includes the compound (b) having the unsaturated double bond and having no hydroxyl group or acidic group, such as a compound (b) such as substituted or unsubstituted styrene, and glycidyl (meth). ) An organic acid (i) having one carboxyl group in one molecule and no ethylenically unsaturated bond in a glycidyl group of a copolymer having an acrylate as a main chain, for example, an alkylcarboxylic acid having 2 to 17 carbon atoms. It is a resin obtained by reacting an acid, an aromatic group-containing alkylcarboxylic acid, or the like, and adding the polybasic acid anhydride (d) to the generated secondary hydroxyl group.

  The carboxyl group-containing resin (7) has a degree of acidity of hydroxyl group-containing polymer (j) such as olefinic hydroxyl group-containing polymer, acrylic polyol, rubber polyol, polyvinyl acetal, styrene allyl alcohol resin, and celluloses. It is a resin having a carboxyl group introduced by reacting the relatively weak polybasic acid anhydride (d).

  On the other hand, in the carboxyl group-containing photosensitive resin (8), the carboxyl group of the carboxyl group-containing resin (7) is reacted with the epoxy group and the epoxy group of the compound (c) having an unsaturated double bond, It is a resin in which an unsaturated double bond of the compound (c) is introduced into a side chain.

  In the synthesis reaction of the carboxyl group-containing photosensitive resin (9), the polyfunctional epoxy compound (g) is reacted with the unsaturated monocarboxylic acid (h) (or compound (k)), and then the compound (k) (or There are a first method of reacting an unsaturated monocarboxylic acid (h) and a second method of simultaneously reacting a polyfunctional epoxy compound (g) with an unsaturated monocarboxylic acid (h) and a compound (k). .. Either method is acceptable, but the second method is preferred.

  Specific examples of the compound (k) having at least two or more hydroxyl groups in one molecule and one other reactive group (eg, carboxyl group, secondary amino group, etc.) other than the hydroxyl group that reacts with the epoxy group Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; dialkanolamines such as diethanolamine and diisopropanolamine.

  On the other hand, in the synthesis reaction of the unsaturated group-containing polycarboxylic acid urethane resin (10), the reaction product (I) is reacted with the polybasic acid anhydride (d), and then the produced unsaturated group-containing polycarboxylic acid It is preferable to react the unsaturated group-containing monoisocyanate (m) with the hydroxyl group in the carboxylic acid resin.

  Specific examples of the unsaturated monoisocyanate (m) include methacryloyl isocyanate, methacryloyloxyethyl isocyanate, and organic diisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) and the above-mentioned 1 molecule. Examples thereof include reaction products obtained by reacting (meth)acrylates having one hydroxyl group in an approximately equimolar ratio.

  The above-mentioned (11) carboxyl group-containing photosensitive resin is a polyfunctional oxetane compound using a compound having an oxetane ring as a starting material, instead of an epoxy resin which mainly produces a secondary hydroxyl group by a reaction with an unsaturated monocarboxylic acid. By reacting the compound (n) with an unsaturated monocarboxylic acid (h) and further reacting the primary hydroxyl group of the obtained modified oxetane resin with a polybasic acid anhydride (d), the binding site is thermally It is a resin that is not easily cut into pieces and has excellent thermal stability.

  The carboxyl group-containing resins of (12) and (13) are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol. -Type epoxy resin, bixylenol-type epoxy resin and other bis-epoxy compounds (p) and carboxylic acid (q) such as oxalic acid, malonic acid, succinic acid, phthalic acid and isophthalic acid, or bisphenols such as bisphenol A and bisphenol F An unsaturated double bond is introduced into the reaction product with (r), and then the secondary hydroxyl group generated in the above reaction or the remaining hydroxyl group is further reacted with polybasic acid anhydride (d). As a result, the resin has excellent thermal stability. The introduction of the unsaturated double bond is generally carried out by reacting an ethylenically unsaturated group such as a vinyl group, an allyl group and a (meth)acryloyl group with a hydroxyl group remaining in the above reaction, a carboxyl group and the like or a generated hydroxyl group. It is carried out by reacting a compound having a reactive group such as an epoxy group and an acid chloride.

  The carboxyl group-containing photosensitive resin (14) has excellent flexibility and elongation due to chain extension of the novolac type phenolic resin (s) by the addition reaction of the alkylene oxide (t), and is produced by the addition reaction of the alkylene oxide. The unsaturated monocarboxylic acid (h) and the polybasic acid anhydride (d) are added to the terminal hydroxyl groups, and the unsaturated group and the carboxyl group do not exist on the same side chain, and each side chain Since it is located at the terminal, the compound has excellent reactivity, and also has excellent alkali developability due to the presence of a terminal carboxyl group distant from the main chain. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran.

  The acid value of the carboxyl group-containing compound (A) as described above is preferably 20 to 200 mgKOH/g, more preferably 50 to 120 mgKOH/g. When the acid value is lower than 20 mgKOH/g, the solubility in an alkaline aqueous solution becomes poor and the formed coating film becomes difficult to develop. On the other hand, when it is higher than 200 mgKOH/g, the surface of the exposed portion is developed regardless of the exposure condition, which is not preferable.

  Further, the carboxyl group-containing compounds (carboxyl group-containing resin and carboxyl group-containing photosensitive resin) as described above can be used alone or in combination of two or more kinds.

  The proportion of the tetra(meth)acrylate compound (B) is appropriately 5 to 100 parts by mass (as solid content, the same applies below) with respect to 100 parts by mass of the carboxyl group-containing compound (A), and is preferable. Is a ratio of 10 to 50 parts by mass. When the compounding ratio of the tetra(meth)acrylate compound (B) is less than 5 parts by mass, it is difficult to obtain sufficient photocurability and/or thermosetting property, and when it exceeds 100 parts by mass, a cured product is obtained. The characteristics are not further improved, and an excessive amount is added, which is economically unfavorable.

  The curable composition of the present invention includes 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate, an aliphatic dicarboxylic acid chloride or an aliphatic dicarboxylic acid or an anhydride thereof, or an aliphatic dicarboxylic acid ester. An unreacted monomer at the time of esterification reaction with and a by-product such as a produced di(meth)acrylate compound or a polymer may be contained.

  The tetra(meth)acrylate compound used in the present invention can be cured by simply heating it and also by irradiation with X-rays or electron beams, but the polymerization initiator (C) (photoradical polymerization initiator (C1 ), a radical polymerization is rapidly carried out by irradiation with an active energy ray and/or heating in the presence of a thermal radical polymerization initiator (C2)), and therefore it is preferable to use such a polymerization initiator.

  As the photoradical polymerization initiator (C1), a known compound that generates a radical upon irradiation with an active energy ray can be used, and specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. Benzoin and benzoin alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; 2-methyl-1-[ 4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, N,N-dimethylaminoacetophenone and the like. Aminoacetophenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 , 4-diisopropylthioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; 2,4,5-triarylimidazole dimer; riboflavin tetrabutyrate; 2-mercaptobenzimidazole, 2-mercaptobenzo Thiol compounds such as oxazole and 2-mercaptobenzothiazole; organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol and tribromomethylphenyl sulfone; benzophenone, 4,4 Examples include benzophenones such as'-bis(diethylamino)benzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. These known and commonly used photoradical polymerization initiators can be used alone or as a mixture of two or more kinds, and further, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4 are used. -Photoinitiating aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine and the like can be added. Further, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to accelerate the photoreaction. Particularly preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-. Examples thereof include dimethylamino-1-(4-morpholinophenyl)-butan-1-one, but are not particularly limited thereto. They absorb light in the ultraviolet light or visible light region, and (meth)acryloyl group As long as it can radically polymerize an unsaturated group, it is not limited to the photopolymerization initiator and the photoinitiator aid, and can be used alone or in combination.

  Examples of the thermal radical polymerization initiator (C2) include benzoyl peroxide, cumene peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, and 2,5-dimethyl-2,5-di(t-). Butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, organic peroxides such as t-butylperoxy-2-ethylhexanoate; 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4- Methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2 ,4-divaleronitrile, 1,1′-azobis(1-acetoxy-1-phenylethane), 1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4, Examples thereof include azo initiators such as 4′-azobis-4-cyanobaric acid and 2-methyl-2,2′-azobispropanenitrile.

  The amount of the above-mentioned polymerization initiator (C) to be blended is sufficient in the usual quantitative ratio, but in the case of the photoradical polymerization initiator with respect to 100 parts by mass of the carboxyl group-containing compound (A), A proportion of 0.5 to 25 parts by mass, and in the case of a thermal radical polymerization initiator, a proportion of 0.1 to 10 parts by mass is preferable.

  Examples of the diluent solvent (D) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol Acetic acid esters such as monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol, propylene glycol, etc. Alcohols; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more kinds. The purpose of using these diluted solvents is to dissolve the carboxyl group-containing compound (A) and the like and to adjust the composition to have a viscosity suitable for the coating method. The compounding amount of the diluting solvent (D) can be any amount depending on the coating method.

Examples of the compound (E) having two or more cyclic ethers in one molecule include an oxirane compound, an oxetane compound and an oxolane compound.
Examples of the oxirane compound include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Tohto manufactured by Dainippon Ink and Chemicals, Inc. Epotote YD-011, YD-013, YD-127, Y6-128 manufactured by Kasei Co., Ltd., and D.C. manufactured by Dow Chemical Co., Ltd. E. R. 317, D.I. E. R. 331, D.I. E. R. 661, D.I. E. R. 664, bisphenol A type epoxy resin such as Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all are trade names) manufactured by Sumitomo Chemical Co., Ltd.; manufactured by Japan Epoxy Resin Co., Ltd. Epicoat YL903, Epichron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Inc., Epotote YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., D.C. manufactured by Dow Chemical Co., Ltd. E. R. Brominated epoxy resins such as 542, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESB-400, ESB-700 (all are trade names); Epicoat 152, Epicoat 154, Dow Chemical (Japan Epoxy Resin Co., Ltd.) D. Co., Ltd. E. N. 431, D.I. E. N. 438, Epiclon N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink and Chemicals, Inc., Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd.'s Sumi-epoxy ESCN-195X, ESCN-220 (all are trade names) and other novolac type epoxies. Resin: Epichron 830 manufactured by Dainippon Ink and Chemicals, Inc., Epicoat 807 manufactured by Japan Epoxy Resins Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (all are trade names) Bisphenol F type epoxy resin such as; Tohto Kasei Co., Ltd. hydrogenated bisphenol A type epoxy resin such as Epotote ST-2004, ST-2007, ST-3000 (all are trade names); Japan Epoxy Resin Co., Ltd. Epikote 604, Toho Kasei Co., Ltd. Epotote YH-434, Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120 (all are trade names), etc.; glycidyl amine type epoxy resin; Daicel Chemical Industries Ltd. Alicyclic epoxy resins such as Celoxide 2001 (trade name) manufactured by Japan; YL-933 manufactured by Japan Epoxy Resins Co., Ltd., EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (both are trade names), etc. Trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Japan Epoxy Resins Co., Ltd. or other bixylenol type or biphenol type epoxy resins or mixtures thereof; Japan. Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Co., Ltd., and EXA-1514 (both are trade names) manufactured by Dainippon Ink and Chemicals, Inc.; Bisphenol A novolac type epoxy resin such as Epicoat 1573 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; tetraphenylolethane type epoxy resin such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; Nissan Heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Kagaku Kogyo Co., Ltd.; Diglycidyl phthalate resin such as Bremmer DGT (trade name) manufactured by NOF CORPORATION; ZX-1063 manufactured by Tohto Kasei Co., Ltd. (Trade name) tetraglycidyl xylenoylethane resin; ESN-190 manufactured by Nippon Steel Chemical Co., Ltd. , ESN-360, HP-4032 manufactured by Dainippon Ink and Chemicals, Inc., EXA-4750, EXA-4700 (all are trade names), and other naphthalene group-containing epoxy resins; manufactured by Dainippon Ink and Chemicals Co., Ltd. Epoxy resins having a dicyclopentadiene skeleton such as HP-7200, HP-7200H (both are trade names); CP-503, CP-50M (both are trade names) manufactured by NOF CORPORATION Polymerization type epoxy resin; further, hydantoin type epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymerized epoxy resin, and alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin , A polyfunctional epoxy resin obtained by reacting epihalohydrin (International Publication WO01/024774), and the like.

  Examples of the oxetane compound include 3,7-bis(3-oxetanyl)-5-oxa-nonane and 3,3′-(1,3-(2-methylenyl)propanediylbis(oxymethylene))bis-( 3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3- Bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol Bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane Tris(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris (3-Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether and the like can be mentioned.

  The above-mentioned compound (E) having two or more cyclic ethers in one molecule can be used alone or in combination of two or more kinds. The compounds having these cyclic ethers are cured by heat to improve properties such as adhesiveness and heat resistance of the resist. The amount of the compound is 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing compound (A), and preferably 15 to 60 parts by mass. When the compounding amount of the compound (E) having a cyclic ether is less than the above range, the cured film has high hygroscopicity, and the PCT resistance tends to decrease, or the heat resistance and electroless plating resistance tend to decrease. On the other hand, when it exceeds the above range, the developability of the coating film and the resistance of the cured film to electroless plating deteriorate, and the PCT resistance also deteriorates.

  Examples of the curing catalyst (F) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. , Imidazole derivatives such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N -Amine compounds such as dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine can be used. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N manufactured by San-Apro Co., Ltd., Examples thereof include U-CAT3502T (all are trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof). In particular, as long as it improves the thermosetting property, it is not limited to these, as long as it is a curing catalyst of a compound having a cyclic ether, or a compound that promotes the reaction of a compound having a cyclic ether and a carboxylic acid, You may use it individually or in mixture of 2 or more types. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, which also functions as an adhesion promoter, 2 It is also possible to use S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct. Preferably, these compounds are used in combination with the curing catalyst. The compounding amount of the above curing catalyst is sufficient in a usual quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing compound (A). It is the ratio of parts.

  Examples of the radical-polymerizable monomer (G) include hydroxyl group-containing acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; polyethylene. Water-soluble acrylates such as glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; trimethylolpropane, hydrogenation Acrylates of ethylene oxide adducts and/or propylene oxide adducts of polyfunctional alcohols such as bisphenol A or polyphenols such as bisphenol A and biphenol; polyfunctional or monofunctional polyurethane acrylates which are isocyanate modified products of the above-mentioned hydroxyl group-containing acrylates Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or epoxy acrylates which are (meth)acrylic acid adducts of phenol novolac epoxy resin, and methacrylates corresponding to the above acrylates. Or two or more kinds can be used in combination. Among these, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule are preferable. The purpose of using these radically polymerizable monomers is to increase the photoreactivity of the composition. The radical-polymerizable monomer that is liquid at room temperature not only serves to increase the photoreactivity of the composition, but also serves to adjust the composition to have a viscosity suitable for various coating methods and to aid solubility in an alkaline aqueous solution. The blending amount of the radically polymerizable monomer (G) is preferably 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing compound (A).

  An inorganic thickener can be added to the curable composition of the present invention to the extent that the properties of the cured product are not deteriorated. As the inorganic thickener, for example, hydrophilic silica such as #50, #200 and #380 manufactured by Nippon Aerosil Co., hydrophobic silica such as #R974 and #R972 manufactured by Nippon Aerosil Co., Ltd., manufactured by Wilber Ellis Co. Examples include organic bentonites such as Orben and Benton 38. The blending amount of these inorganic thickeners is sufficient in a usual quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing compound (A). The ratio is 0.0 part by mass.

  The curable composition of the present invention further, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, Known and commonly used inorganic fillers such as magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica, rubber fine particles, powdered epoxy resin (for example, TEPIC manufactured by Nissan Chemical Industries, Ltd.), urethane resin, melamine resin, benzoguanamine resin Organic substances such as (for example, M-30, S, MS, etc. manufactured by Nippon Shokubai Co., Ltd.), urea resin, crosslinked acrylic polymer (for example, MR-2G, MR-7G manufactured by Soken Chemical Co., Ltd., techpolymer manufactured by Sekisui Plastics Co., Ltd.) The filler may be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion, hardness and heat resistance. A suitable amount of the filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the carboxyl group-containing compound (A).

  The curable composition of the present invention, if necessary further known phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other known colorants, hydroquinone, Hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, and other commonly known thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based defoaming agents and/or leveling agents, imidazole-based, thiazole-based, triazole-based Well-known and commonly used additives such as silane coupling agent and the like can be added.

Further, the curable composition of the present invention may contain a flame retardant such as a halogen-based flame retardant, a phosphorus-based flame retardant, and an antimony-based flame retardant for the purpose of obtaining flame retardancy. The amount of the flame retardant compounded is usually 1 to 200 parts by mass, preferably 5 to 50 parts by mass, relative to 100 parts by mass of the carboxyl group-containing compound (A). When the blending amount of the flame retardant is within the above range, the flame retardancy, heat resistance, water resistance and adhesion of the resulting cured product are highly balanced, which is preferable.
Water may also be added to reduce the flammability of the composition of the present invention and to increase the viscosity.

  The curable composition of the present invention can be easily cured to obtain a cured product by photocuring and/or heat curing in the same manner as a conventionally known method. For example, the curable composition is sufficiently mixed by using a roll until it becomes uniform, and a desired substrate depending on the application, for example, a known method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. It is possible to form a coating film which is excellent in dryness to the touch without causing sagging by applying the coating method described in (1) and volatilizing and drying the diluted solvent contained in the composition at a temperature of about 60 to 100° C. .. Further, the curable composition of the present invention can form a dry film for resist, and in that case, it may be laminated as it is. After that, it is exposed to an active energy ray to be photocured. Then, by heat curing at about 100° C. to 200° C., in addition to excellent crack resistance, various properties such as electric insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance, etc. An excellent cured product can be obtained. In the case of forming a solder resist of a printed wiring board, it is selectively exposed to an active energy ray such as ultraviolet rays through a photomask having a pattern, or is directly drawn by a laser beam, and an unexposed portion is developed with a dilute alkaline aqueous solution. By forming a resist pattern and curing it by heating, a resist film having excellent properties as described above can be obtained. Examples of the dilute alkaline aqueous solution used for the development include aqueous solutions of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following, "parts" means "parts by mass" unless otherwise specified.

Synthesis example 1
In a 100 ml flask equipped with a nitrogen introduction tube and a thermometer, 10.0 g (46.68 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A), 80 ml of tetrahydrofuran , Terephthalic acid chloride 4.7 g (23.34 mmol), triethylamine 5.9 g (58.35 mmol), 4-dimethylaminopyridine 0.5 g (4.09 mmol), methylhydroquinone 0.4 mg were added, and a nitrogen stream was added. Under reflux at 65° C. for 20 hours. After adding 50 ml of water to the reaction solution to dissolve the basic salt of triethylamine in water, the reaction mixture was extracted with ethyl acetate. Furthermore, the reaction mixture in the aqueous layer was extracted with 25 ml of ethyl acetate. The obtained organic layer was washed with 50 ml of a 1N aqueous hydrochloric acid solution and subsequently with 50 ml of saturated saline. The organic layer was dried over 5.0 g of sodium sulfate, filtered under reduced pressure and concentrated to obtain 11.7 g of a compound. This product was subjected to column purification using 230 g of neutral silica gel. As a result, 4.5 g of a tetra(meth)acrylate compound was obtained. This was a yield of 34.5% of theory. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained tetra(meth)acrylate compound, nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatography Grams (measured using high performance liquid chromatography) are shown in FIGS. 1, 2 and 3, respectively. Table 1 shows the ¹ H-NMR identification results. In addition, since only one peak appears in the chromatogram shown in FIG. 3, it can be seen that a pure compound was obtained.

Synthesis example 2
1.0 g (4.67 mol) of 3-acryloyloxy-2-hydroxypropyl methacrylate (Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A), tetrahydrofuran in a 10-liter flask equipped with a nitrogen inlet tube and a thermometer. 7.0 liter, 475.0 g (2.34 mol) of terephthaloyl chloride, 590 g (5.83 mol) of triethylamine, 0.4 g of methylhydroquinone and 0.4 g of phenothiazine were added and reacted at room temperature for 6 hours under a nitrogen stream. It was After adding 5.0 liters of water to the reaction solution to dissolve the basic salt of triethylamine in water, the reaction mixture was extracted with 5.0 liters of ethyl acetate. Furthermore, the reaction mixture in the aqueous layer was extracted with 2.5 liters of ethyl acetate. The obtained organic layer was washed with 5.0 L of a 1N hydrochloric acid aqueous solution, subsequently with 5.0 L of a saturated aqueous sodium hydrogen carbonate solution, and further with 5.0 L of a saturated saline solution. The obtained organic layer was dried over 500 g of magnesium sulfate, filtered under reduced pressure and concentrated to obtain 1.5 kg of a reaction concentrated mixture (viscous yellow liquid). After 2.5 liters of methanol was added to the obtained reaction concentrated mixture to make it homogeneous, the mixture was cooled to -30°C to form crystals, which was filtered (washed with methanol) and filtered to give white tetra( 350 g of a meth)acrylate compound was obtained. This was a yield of 27.0% of theory. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained tetra(meth)acrylate compound, nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatography Grams (measured using high performance liquid chromatography) are shown in FIGS. 4, 5 and 6, respectively.

Test example 1
The white crystalline tetra(meth)acrylate compound was melted at 100° C., and applied on a polyimide film with a bar coater to a thickness of 50 μm, and (1) 120° C. for 120 minutes, (2) 140 The temperature is 30° C. for 30 minutes, (3) 160° C. for 20 minutes, or (4) 180° C. for 10 minutes, and then 121° C. and 100% RH using a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412MD). For 24 hours and then the cured film was peeled off from the polyimide film to obtain four types of evaluation samples. The heat resistance, flexibility and folding endurance of these evaluation samples were measured by the methods described below to evaluate the degree of thermal deterioration under high humidity. Further, a cured film was prepared in the same manner as above except that the treatment with the PCT apparatus was not performed on the glass plate whose mass was measured in advance, and an evaluation sample was obtained. The water absorption of this cured film was measured and evaluated by the method described below. The measurement results are shown in Table 2 below.

上記表２中の性能試験の評価方法は以下の通りである。

The evaluation method of the performance test in Table 2 above is as follows.

(1) Heat resistance The sample was evaluated by thermogravimetry (TG) to evaluate the heat resistance.
In this specification, the extrapolation point obtained from the tangent line at the inflection portion of the TG curve as shown in FIG.

(2) Flexibility By processing the evaluation sample into a width of 10 mm and a length of 90 mm, one side of the film-shaped test piece is placed on an electronic scale, and the other side is bent to reduce the distance between the films to 10 mm. By the maximum load applied to the electronic scale until reaching, the repulsive force was evaluated according to the following criteria.
◯: Less than 10 g △: 10 to less than 30 g ×: 30 g or more, or broken material and unmeasurable

(3) Folding resistance A film-shaped test piece produced by processing the evaluation sample into a width of 10 mm and a length of 90 mm was bent at 135° and evaluated according to the following criteria.
◯: The cured film does not break Δ: The cured film does not break but has cracks ×: The cured film breaks

(4) Water Absorption Rate The mass of the evaluation sample was measured, and then this evaluation sample was treated for 24 hours at 121° C. and 100% RH using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD), and after the treatment. The mass of the cured product was measured, and the water absorption of the cured product was determined by the following formula.
Water absorption _{(%) = {(W 2} -W 1) / (W 1 -W g)} × 100
Here, W ₁ is the mass of the evaluation sample, W ₂ is the mass of the evaluation sample after the PCT treatment, and W _g is the mass of the glass plate.

Preliminary Synthesis Example 1
A 1-liter flask was charged with 40 g (0.185 mol) of 2,6-naphthalenedicarboxylic acid and 120 ml (1.67 mol) of thionyl chloride, and heated under reflux at about 80° C. for 1 hour under an argon stream. Then, 1 ml of dimethylformamide was added, and the mixture was further heated and refluxed at about 80° C. for 24 hours. After completion of the reaction, unreacted thionyl chloride was distilled off under reduced pressure to obtain 31.0 g of yellow crystals of 2,6-naphthalenedicarboxylic acid chloride.

Preliminary synthesis example 2
A 1-liter flask was charged with 80 g (0.37 mol) of 2,6-naphthalenedicarboxylic acid, 240 ml (3.3 mol) of thionyl chloride and 2 ml of pyridine, and heated under reflux at about 80° C. for 1 hour under an argon stream. .. Then, 1 ml of dimethylformamide was added, and the mixture was further heated and refluxed at about 80° C. for 4 hours. Subsequently, 100 ml of thionyl chloride was added, and the mixture was heated under reflux at about 80° C. for 14.5 hours. After completion of the reaction, unreacted thionyl chloride was distilled off under reduced pressure to obtain 73.8 g of yellow crystals of 2,6-naphthalenedicarboxylic acid chloride.

Preliminary Synthesis Example 3
53.8 g of 2,6-naphthalenedicarboxylic acid chloride obtained in Preliminary Synthesis Example 2 was dissolved in toluene, cooled at -30°C for 12 hours, and the precipitated crystals were filtered to obtain highly pure 2,6-naphthalene. 22.7 g of dicarboxylic acid chloride was obtained.

Synthesis example 3
3-acryloyloxy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A) 43.3 g (202 mmol), tetrahydrofuran 400 ml, phenothiazine 4.3 mg, triethylamine 51. 1 g (505 mmol) was charged and the mixture was stirred at about 0° C. under an argon stream. Next, 19 g (80 mmol) of 2,6-naphthalenedicarboxylic acid chloride obtained in Preliminary Synthesis Example 1 was dissolved in 200 ml of tetrahydrofuran and added dropwise into the reaction system at 10°C or lower. After completion of the dropping, the temperature in the reaction system was set to about 25° C. and the reaction was carried out for 2 hours. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl ether. The separated organic layer was washed with water and then with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated to obtain 57 g of a brown oil. The chromatogram of the obtained oil (measured using high performance liquid chromatography) is shown in FIG. Next, the obtained oil was subjected to column purification (SiO ₂ : 200 g, developing solvent: 40% ethyl acetate/n-hexane) to obtain 2.5 g of a yellow oil. 10 ml of methanol was added to the obtained oil, the mixture was cooled at -30°C for 5 hours, and filtered to obtain 1.5 g of white crystals. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatography of the obtained tetra(meth)acrylate compound Grams (measured using high performance liquid chromatography) are shown in FIGS. 9, 10 and 11, respectively.

Synthesis example 4
A 1-liter flask was charged with 28.3 g (79 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate, 230 ml of tetrahydrofuran, 2.0 mg of phenothiazine, and 24.0 g (237 mmol) of triethylamine at about 0° C. under an argon stream. It was stirred. Next, 20.0 g (79 mmol) of 2,6-naphthalenedicarboxylic acid chloride obtained in Preliminary Synthesis Example 2 was dissolved in 200 ml of tetrahydrofuran and added dropwise into the reaction system at 10° C. or lower. After completion of the dropping, the temperature in the reaction system was set to about 25° C. and the reaction was performed for 2 hours. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The separated organic layer was washed with water and then saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated to obtain 37 g of a brown oil. The chromatogram of the obtained oil (measured using high performance liquid chromatography) is shown in FIG. The obtained oil was subjected to column purification (SiO ₂ : 320 g, developing solvent: in 20% ethyl acetate/n-hexane) to obtain 14.0 g of a colorless transparent liquid. 20 ml of ethyl ether was added to the obtained oil, 4 mg of the white crystal obtained in Synthesis Example 3 was added as a seed crystal, and recrystallization was performed at -30°C for 12 hours. As a result, a white semi-solid substance was obtained. Therefore, ethyl ether was removed, then n-hexane was added, and after stirring, the mixed solvent of ethyl ether and n-hexane that could not be removed was removed, 20 ml of ethyl ether was added again, and the mixture was filtered. 2.7 g of white crystals having a melting point of about 92° C. were obtained. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained tetra(meth)acrylate compound, nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatography Grams (measured using high performance liquid chromatography) are shown in FIGS. 13, 14 and 15, respectively. Table 3 shows the ¹ H-NMR identification results.

Further, the above filtrate was concentrated to obtain 11.3 g of a colorless transparent liquid. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained liquid, nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatogram (high performance liquid chromatography). 16) is shown in FIGS. 16, 17 and 18, respectively.

Synthesis example 5
A 1-liter flask was charged with 38.4 g (179 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate, 230 ml of tetrahydrofuran, 2.5 mg of phenothiazine, and 27.2 g (269 mmol) of triethylamine at about 0° C. under an argon stream. It was stirred. Then, 22.7 g (90 mmol) of 2,6-naphthalenedicarboxylic acid chloride obtained in Preliminary Synthesis Example 3 was dissolved in 360 ml of tetrahydrofuran and added dropwise into the reaction system at 10° C. or lower. After completion of the dropping, the temperature in the reaction system was set to about 25° C. and the reaction was carried out for 2 hours. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The separated organic layer was washed with water and then a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated to obtain 60.1 g of a brown oil. The chromatogram of the obtained oil (measured using high performance liquid chromatography) is shown in FIG. Next, the obtained oil was subjected to column purification (SiO ₂ : 500 g, developing solvent: in 20% ethyl acetate/n-hexane) to obtain 25.2 g of a colorless transparent oil. 70 ml of ethyl ether was added to the obtained oil, and the mixture was stirred and then filtered to obtain 6.6 g of white crystals. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained tetra(meth)acrylate compound, nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and chromatography Grams (measured using high performance liquid chromatography) are shown in FIGS. 20, 21 and 22, respectively.

Test example 2
Each of the white crystalline tetra(meth)acrylate compounds obtained in Synthesis Examples 1 to 3 was melted at 100° C. and applied to a polyimide film with a bar coater to a thickness of 50 μm, and the mixture was heated at 180° C. for 30 minutes. Then, it was heated at 200° C. for 10 minutes. The obtained cured film was treated for 24 hours at 121° C. and 100% RH using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD), and then the cured film was peeled from the polyimide film to obtain an evaluation sample. The heat resistance of these evaluation samples was measured by the method (1) used in Test Example 1, and the flexibility and folding endurance were measured and evaluated by the methods described below. Further, a cured film was prepared in the same manner as above except that the treatment with the PCT apparatus was not performed on the glass plate whose mass was measured in advance, and an evaluation sample was obtained. The water absorption of this cured film was measured and evaluated by the method (4) used in Test Example 1 above. The measurement results are shown in Table 4 below.

上記表４中の性能試験の柔軟性及び耐折性の評価方法は以下の通りである。

The evaluation methods for the flexibility and folding endurance of the performance test in Table 4 above are as follows.

(2′) Flexibility A film-shaped test piece manufactured by processing the evaluation sample into a width of 5 mm and a length of 40 mm is placed on an electronic scale, and the other side is bent, and the distance between the films is 10 mm. The maximum load applied to the electronic scale until it became the repulsive force was evaluated according to the following criteria.
◯: less than 10 g Δ: 10 to less than 30 g ×: 30 g or more, or the test piece is broken and cannot be measured

(3′) Folding resistance A film-like test piece produced by processing the evaluation sample into a width of 5 mm and a length of 40 mm was bent at 135° and evaluated according to the following criteria.
◯: The cured film does not break Δ: The cured film does not break but has cracks ×: The cured film breaks

Synthesis example 6
In a 50 ml flask, 2.0 g (9.33 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate (Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A), 20 ml of N,N-dimethylformamide, 4 -Tert-butyl catechol 1 mg, 1-hydroxy-1-H-benzotriazole hydrate 1.71 g (11.2 mmol), triethylamine 2.4 g (23.34 mmol), 1-ethyl-3-(3- Dimethylaminopropyl)carbodiimide hydrochloride (2.2 g, 11.2 mmol) and succinic acid (826 mg, 7 mmol) were added, and the mixture was reacted at room temperature for 14 hours while stirring under an argon stream. Ethyl acetate and water were added to the obtained reaction solution for extraction, the separated organic layer was washed with saturated brine, dried over magnesium sulfate, filtered and concentrated to give 2.3 g of a yellow liquid. Obtained. This product was subjected to column purification using 50 g of silica gel to obtain 1.5 g of a liquid mixture of a tetra(meth)acrylate compound having an acid value of 1 mgKOH/g or less and 3-acryloyloxy-2-hydroxypropyl methacrylate.

The resulting tetra (meth) acrylate compound and 3-acryloyloxy-2-hydroxy-nuclear magnetic resonance spectrum of a mixture of propyl methacrylate (solvent CDCl _3, standard substance TMS (tetramethylsilane)), a chromatogram (HPLC 23), and an infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) are shown in FIGS. 23, 24, and 25, respectively. Table 5 shows the ¹ H-NMR identification results.

For reference, a nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) and a chromatogram (measured using high performance liquid chromatography) of 3-acryloyloxy-2-hydroxypropyl methacrylate alone are shown. 26 and 27, and FIG. 28 shows a nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) of a monocarboxylic acid having a structure represented by the following formula (3).

（但し、Ｒ^１、Ｒ^２は水素原子又はメチル基を表わす。）

(However, R ¹ and R ² represent a hydrogen atom or a methyl group.)

  Comparing FIG. 23 and FIG. 26, in the mixture of the above tetra(meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate, a single peak of succinic acid which is not found in 3-acryloyloxy-2-hydroxypropyl methacrylate is obtained. It appears around 2.6 ppm. Also, comparing FIG. 23 and FIG. 28, in the monocarboxylic acid, the single peak of the carboxylic acid which is not in the mixture of the tetra(meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate is 10.3 ppm. It appears in the vicinity. Further, comparing FIG. 24 and FIG. 27, in the mixture of the tetra(meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate, a peak not found in 3-acryloyloxy-2-hydroxypropyl methacrylate was 6 minutes. It appears in the vicinity. From the above data, the peak appearing at around 6 minutes in FIG. 24 is due to the above-mentioned tetra(meth)acrylate compound.

Synthesis example 7
In a 50 ml flask, 1.71 g (8 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate (Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A), tetrahydrofuran 20 ml, 4-methoxyphenol 0.8 mg, triethylamine 2 0.02 g (20 mmol) was charged, 1.02 g (5.6 mmol) of adipic acid chloride was added dropwise with stirring at 0° C. under an argon stream, and after completion of the reaction, the reaction was carried out at room temperature for about 14 hours. After completion of the reaction, the reaction solution was filtered, and saturated aqueous sodium hydrogen carbonate solution and diethyl ether were added for extraction. Then, the separated organic layer was dried over sodium sulfate, filtered, concentrated, and then subjected to column purification (40 g of silica gel, developing solvent: 20% ethyl acetate/n-hexane) to give a colorless transparent oily tetra( A liquid mixture of a (meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate was obtained. The nuclear magnetic resonance spectrum (solvent CDCl ₃ , standard substance TMS (tetramethylsilane)) of the obtained mixture is shown in FIG. 29. Table 6 shows the ¹ H-NMR identification results.

Synthesis example 8
In a 50 ml flask, 1.71 g (8 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate (Shin-Nakamura Chemical Co., Ltd., trade name NK ester 701A), 20 ml of tetrahydrofuran, 0.8 mg of 4-methoxyphenol, triethylamine 2 0.02 g (20 mmol) was charged, 1.02 g (5.6 mmol) of adipic acid chloride was added dropwise with stirring at 0° C. under an argon stream, and after completion of the reaction, the reaction was carried out at room temperature for about 13 hours. After the reaction was completed, the reaction solution was filtered, subjected to a short column treatment (25 g of silica gel, a developing solvent: tetrahydrofuran) and concentrated to give a mixture of a tetra(meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate of about 64. %, 2.5 g of liquid mixture was obtained. Nuclear magnetic resonance spectrum (solvent CDCl ₃ , reference substance TMS (tetramethylsilane)) of a mixture of the obtained tetra(meth)acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate, a chromatogram by gel permeation chromatography, and Infrared absorption spectra are shown in FIGS. 30, 31 and 32, respectively. For reference, a chromatogram obtained by gel permeation chromatography of 3-acryloyloxy-2-hydroxypropyl methacrylate alone is shown in FIG.

Test example 3
A liquid mixture of the tetra(meth)acrylate compound of Synthesis Examples 6 and 8 and 3-acryloyloxy-2-hydroxypropyl methacrylate was formed into a polyethylene terephthalate film using a bar coater so as to have a thickness of 50 μm. It is applied and heated at 180° C. for 30 minutes to peel off the cured coating film from the polyethylene terephthalate film, and then treated for 24 hours under the conditions of 121° C. and 100% RH using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD). , An evaluation sample was obtained. The heat resistance of these evaluation samples was measured by the method (1) used in Test Example 1, the folding endurance was measured by the method (3′) used in Test Example 2, and the flexibility is described later. It was measured by the method, and the degree of thermal deterioration under high humidity was evaluated. Further, a cured film was prepared in the same manner as above except that the treatment with the PCT apparatus was not performed on the glass plate whose mass was measured in advance, and an evaluation sample was obtained. The water absorption of this cured film was measured and evaluated by the method (4) used in Test Example 1 above. The above measurement results are shown in Table 7 below.

上記表５中の性能試験の柔軟性の評価方法は以下の通りである。

The method of evaluating the flexibility of the performance test in Table 5 above is as follows.

(2″) Flexibility A film-shaped test piece prepared by processing the evaluation sample into a width of 5 mm and a length of 40 mm was placed on an electronic scale, and the other side was bent, and the distance between the films was 10 mm. The maximum load applied to the electronic scale until it became the repulsive force was evaluated according to the following criteria.
◯: less than 20 g Δ: 20 to less than 40 g x: 20 g or more, or the test piece is broken and cannot be measured

Examples 1-5 and Comparative Examples 1, 2
Each component was blended according to the blending composition shown in Table 8 (numerical values are parts by mass). Each of Examples 1 to 3 was stirred at 90° C., Example 4 was stirred at room temperature, and Example 5 was stirred at 100° C. to prepare curable compositions. For Comparative Examples 1 and 2, a curable composition was prepared by kneading each separately with a three-roll mill. These were applied to a polyimide film using a bar coater so as to have a thickness of 50 μm, and for Examples 1 to 3 and Comparative Examples 1 and 2, exposure was performed under the condition of an exposure amount of 300 mJ/cm ^2. The sample No. 4 was left standing at room temperature for 6 hours and then gradually heated to 115° C. over 60 minutes and heated at 115° C. for 60 minutes, and the sample No. 5 was heated at 180° C. for 30 minutes and then 200° C. for 10 minutes. .. Next, a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD) was used for treatment at 121° C. and 100% RH for 24 hours, and then the cured film was peeled off from each polyimide film to obtain an evaluation sample.

Examples 6 and 7
In Example 6, the composition obtained in Example 1 was melted at 100° C., impregnated in glass cloth, and then exposed under the condition of an exposure amount of 300 mJ/cm ² , and in Example 7, The tetra(meth)acrylate compound obtained in Synthesis Example 2 was melted at 100° C., impregnated in a glass cloth, and then heated at 140° C. for 30 minutes, and then a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-). 412MD) and treated at 121° C. and 100% RH for 24 hours to obtain an evaluation sample.

  The heat resistance of the evaluation samples obtained in each of the examples and each of the comparative examples was measured by the method (1) used in the test example 1, and the examples 1 to 4, 6, 7 and the comparative examples 1, 2 were measured. The flexibility and folding endurance of the evaluation sample obtained in Example 5 were measured by the methods (2) and (3) used in Test Example 1, and the flexibility and folding endurance of the evaluation sample obtained in Example 5 were It measured by the method (2') and (3') used in the said test example 2, and evaluated the degree of thermal deterioration etc. under high humidity. Further, a cured film was prepared in the same manner as in the above-mentioned Examples and Comparative Examples except that the treatment with the PCT apparatus was not performed on the glass plate whose mass was measured in advance, to obtain an evaluation sample. The water absorption of this cured film was measured and evaluated by the method (4) used in Test Example 1 above. The results of each of the above tests are shown in Table 9.

Examples 8, 9, 11, 12 and Comparative Examples 3, 4
Each component was blended according to the blending composition shown in Table 10 (numerical values are parts by mass). For Examples 8, 11, and 12 and Comparative Examples 3 and 4, the curable compositions were prepared by stirring the ingredients. About Example 9, it stirred at 90 degreeC and prepared the curable composition. These were applied to a polyethylene terephthalate film using a bar coater so as to have a thickness of 50 μm. For Example 8 and Comparative Examples 3 and 4, exposure was performed under the condition of an exposure amount of 300 mJ/cm ² , and Example 9 was used. For Nos. 12 and 12, heating at 150° C. for 60 minutes, and for Example 11, after standing at room temperature for 6 hours, the temperature was raised to 80° C. over 60 minutes, 80° C. for 30 minutes, then 100° C. for 30 minutes It was then heated at 150° C. for 30 minutes. Next, a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD) was used for treatment for 24 hours at 121° C. and 100% RH, and then the cured film was peeled from each polyethylene terephthalate film to obtain an evaluation sample.

Example 10
For Example 10, after impregnating a glass cloth with the same composition as that of Example 8, the glass cloth was exposed under the condition of an exposure amount of 300 mJ/cm ² , and then, a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412MD) was used. Was used for 24 hours under the conditions of 121° C. and 100% RH to obtain an evaluation sample.

The heat resistance of the evaluation samples obtained in the respective Examples and Comparative Examples was the method (1) used in Test Example 1, and the flexibility and the folding endurance were the method (2′) used in Test Example 2 described above. ) And (3'), respectively, and the degree of thermal deterioration under high humidity was evaluated.
Further, a cured film was prepared on the glass plate whose mass was measured in advance in the same manner as in the above-mentioned Examples and Comparative Examples except that the treatment by the PCT apparatus was not carried out, and an evaluation sample was obtained. The water absorption of this cured film was measured and evaluated by the method (4) used in Test Example 1 above. The results of each of the above tests are shown in Table 11.

Synthesis example 9
In an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, and a stirrer, a novolac type cresol resin (trade name "Shaunol CRG951", Showa Highpolymer Co., Ltd., OH equivalent: 119.4) 119. 4 g, potassium hydroxide 1.19 g and toluene 119.4 g were charged, the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132° C. and 0 to 4.8 kg/cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed to neutralize potassium hydroxide to have a nonvolatile content of 62.1% and a hydroxyl group equivalent of 182.2 g/eq. A propylene oxide reaction solution of the novolac type cresol resin was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of the phenolic hydroxyl group.

  The obtained alkylene oxide reaction solution of novolac type cresol resin 293.0 g, acrylic acid 43.2 g, methanesulfonic acid 11.53 g, methylhydroquinone 0.18 g and toluene 252.9 g were stirred using a stirrer, a thermometer and an air blowing tube. Was charged into a reactor equipped with, and air was blown at a rate of 10 ml/min, and the reaction was carried out at 110° C. for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water was distilled out. Then, the mixture was cooled to room temperature, the obtained reaction solution was neutralized with 35.35 g of a 15% sodium hydroxide aqueous solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolac type acrylate resin solution.

  Next, 332.5 g of the resulting novolac type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min, While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the mixture was reacted at 95 to 101° C. for 6 hours, cooled, and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 70.6% and a solid content acid value of 87.7 mgKOH/g.

Synthesis example 10
A reaction vessel equipped with a gas introduction pipe, a stirrer, a cooling pipe, a thermometer, and a dropping funnel for continuously dropping an aqueous solution of an alkali metal hydroxide had a hydroxyl group equivalent of 80 g/eq. 1,5-dihydroxynaphthalene (224 g) and bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 828, epoxy equivalent 189 g/eq.) 1075 g are charged and dissolved at 110° C. under stirring in a nitrogen atmosphere. It was Thereafter, 0.65 g of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150° C., and the reaction was carried out for about 90 minutes while maintaining the temperature at 150° C., with an epoxy equivalent of 452 g/eq. To obtain the epoxy compound (3-a). Next, the temperature in the flask was cooled to 40° C., 1920 g of epichlorohydrin, 1690 g of toluene, and 70 g of tetramethylammonium bromide were added, and the temperature was raised to 45° C. with stirring and maintained. Thereafter, 364 g of a 48% aqueous sodium hydroxide solution was continuously added dropwise over 60 minutes, and then the reaction was further continued for 6 hours. After completion of the reaction, most of the excess epichlorohydrin and toluene were distilled under reduced pressure to be recovered, and the reaction product containing the by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled off under reduced pressure from the organic solvent layer to obtain an epoxy equivalent of 277 g/eq. To obtain a polynuclear epoxy resin (3-b). In the obtained polynuclear epoxy resin (3-b), when calculated from the epoxy equivalent, about 1.59 of the alcoholic hydroxyl groups of 1.98 in the epoxy compound (3-a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%.

  Next, 277 g of the obtained polynuclear epoxy resin (3-b) was placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 290 g of carbitol acetate was added, and the mixture was heated and dissolved, and 0.46 g of methylhydroquinone, 1.38 g of triphenylphosphine was added and heated to 95 to 105° C., 72 g of acrylic acid was gradually added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90° C., 129 g of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. For the reaction, oxidation of the reaction solution by potentiometric titration and total oxidation are measured, and the reaction is followed by the addition rate obtained, and the reaction rate is 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 62% and a solid content acid value of 100 mgKOH/g.

Examples 13 to 15 and Comparative Examples 5 and 6
The components were blended according to the blending composition shown in Table 12, and each was kneaded separately with a three-roll mill to prepare a curable composition. This is screen-printed using a 100-mesh polyester screen to a total thickness of 20 to 30 μm on a patterned copper through-hole printed wiring board, and the coating film is heated at 80° C. in a hot air drier. For 30 minutes, then apply a negative film having a resist pattern to the coating film, and irradiate it with ultraviolet rays (exposure amount 700 mJ, manufactured by Oak Manufacturing Co., Ltd., model HMW-680GW). /Cm ² ) and developed with a 1 mass% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg/cm ² , and then heat-cured for 60 minutes in a hot air dryer at 150° C. to prepare a test substrate. ..

  The test substrate having the obtained cured film is tested for crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold plating resistance by the test method and evaluation method described below. It was

  Further, a test circuit board was prepared under the same conditions as above using a B pattern of a printed circuit board (thickness: 1.6 mm) defined by IPC instead of the copper through-hole printed wiring board, and an electric insulation resistance test was conducted. . The results of each of the above tests are shown in Table 13.

表１３に示される結果から明らかなように、感光性成分としてカルボキシル基含有感光性樹脂を用いた比較例５、６ではヒートサイクル時の耐クラック性に劣っていたが、本発明に従ってさらにテトラ（メタ）アクリレート化合物を含有する実施例１３〜１５では耐クラック性に優れていた。上記表１３中の性能試験の評価方法は以下の通りである。

As is clear from the results shown in Table 13, Comparative Examples 5 and 6 using the carboxyl group-containing photosensitive resin as the photosensitive component were inferior in crack resistance during heat cycle, but in accordance with the present invention, tetra( In Examples 13 to 15 containing the (meth)acrylate compound, the crack resistance was excellent. The evaluation method of the performance test in Table 13 above is as follows.

(5) Crack resistance:
The crack resistance of the cured film was evaluated according to the following criteria, using Thermal Shock Chamber NT 1020W manufactured by Kusumoto Kasei Co., Ltd., at −65° C. to 150° C. as one cycle.
◯: A crack was generated in 500 cycles or more. Δ: A crack was generated in 300 to 499 cycles. X: A crack was generated in 299 cycles or less.

(6) PCT resistance:
The PCT resistance of the cured film was evaluated according to the following criteria under the conditions of 121° C. and saturated steam for 50 hours.
◯: The cured film has no blistering, peeling or discoloration. Δ: The cured film has some blistering, peeling or discoloration. X: The cured film has blistering, peeling or discoloration.

(7) Adhesion:
According to the test method of JIS D 0202, cross-cuts were put on the cured film in a grid pattern, and then the peeling ability after a peeling test with a cellophane adhesive tape was visually judged.
⊚: 100/100 with no peeling ◯: 100/100 with cross-cut portion slightly peeled Δ: 50/100 to 90/100
X: 0/100 to 50/100

(8) Solder heat resistance:
According to the test method of JIS C 6481, the test substrate was immersed in a solder bath at 260° C. for 10 seconds three times to evaluate the change in appearance. As the post flux (rosin type), a flux according to JIS C 6481 was used.
○: No change in appearance △: Discoloration of the cured film is observed ×: Floating, peeling, and solder dip

(9) Acid resistance:
The test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at 20° C. for 30 minutes and then taken out, and the state of the cured film was evaluated according to the following criteria.
◯: No change was observed Δ: Slightly changed ×: Cured film or swelling loss

(10) Alkali resistance:
The test substrate was evaluated in the same manner as the acid resistance test except that the 10 vol% sulfuric acid aqueous solution was replaced with a 10 mass% sodium hydroxide aqueous solution.

(11) Electroless gold plating resistance:
Electroless gold plating was performed on the test substrate according to the steps described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and the peeled state of the cured film was determined according to the following criteria.
◯: No change in appearance and no peeling of the cured film.
Δ: There is no change in appearance, but the cured film is slightly peeled off.
X: Floating of the cured film is observed, plating dip is recognized, and peeling of the cured film is large in the peeling test.

Electroless gold plating process:
1. Degreasing:
The test substrate was immersed in an acidic degreasing liquid (manufactured by Nippon MacDermid Co., Ltd., 20% by volume Metex L-5B aqueous solution) at 30° C. for 3 minutes.
2. Washing with water:
The test substrate was immersed in running water for 3 minutes.
3. Soft etch:
The test substrate was immersed in a 14.3 mass% ammonium persulfate aqueous solution at room temperature for 3 minutes.
4. Washing with water:
The test substrate was immersed in running water for 3 minutes.
5. Acid immersion:
The test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute.
6. Washing with water:
The test substrate was immersed in running water for 30 seconds to 1 minute.
7. Catalyst application:
The test substrate was immersed in a catalyst liquid (10% by volume of metal plate activator 350, manufactured by Meltex Co., Ltd.) at 30° C. for 7 minutes.
8. Washing with water:
The test substrate was immersed in running water for 3 minutes.
9. Electroless nickel plating:
The test substrate was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melplate Ni-865M, 20% by volume aqueous solution) having a pH of 4.6 at 85° C. for 20 minutes.
10. Acid immersion:
The test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute.
11. Washing with water:
The test substrate was immersed in running water for 30 seconds to 1 minute.
12. Electroless gold plating:
The test substrate was immersed for 10 minutes in a gold plating solution (manufactured by Meltex Co., Ltd., an aqueous solution containing 15% by volume of Aurolectroles UP and 3% by weight of potassium gold cyanide) at 95° C. and pH=6.
13. Washing with water:
The test substrate was immersed in running water for 3 minutes.
14. Yuwashi:
The test substrate was immersed in warm water at 60° C., thoroughly washed with water for 3 minutes, thoroughly washed with water, and dried.
Through these steps, a test substrate plated with electroless gold was obtained.

(12) Electric insulation:
The electrical insulation of the cured film was evaluated according to the following criteria.
Humidification conditions: temperature 110° C., humidity 85% R.V. H. , Applied voltage 5V, 50 hours.
Measurement conditions: measurement time 60 seconds, applied voltage 500V.
◯: Insulation resistance value after humidification 10 ¹⁰ Ω or more, no copper migration Δ: Insulation resistance value after humidification 10 ¹⁰ Ω or more, copper migration x: Insulation resistance value after humidification 10 ⁹ Ω or less, copper migration Yes

Examples 16 to 20 and Comparative Examples 7 and 8
Each component was blended according to the blending composition shown in Table 14, and kneaded separately with a three-roll mill to prepare a curable composition. This is screen-printed using a 100-mesh polyester screen to a total thickness of 20 to 30 μm on a patterned copper through-hole printed wiring board, and the coating film is heated at 80° C. in a hot air drier. For 30 minutes, then apply a negative film having a resist pattern to the coating film, and irradiate it with ultraviolet rays (exposure amount 600 mJ, manufactured by Oak Manufacturing Co., Ltd., model HMW-680GW). /Cm ² ) and developed with a 1 mass% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg/cm ² , and then heat-cured for 60 minutes in a hot air dryer at 150° C. to prepare a test substrate. .

  The test substrate having the obtained cured film is tested for crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold plating resistance by the above-described test method and evaluation method. It was

  Further, a test circuit board was prepared under the same conditions as above using a B pattern of a printed circuit board (thickness: 1.6 mm) defined by IPC instead of the copper through-hole printed wiring board, and an electric insulation resistance test was conducted. .

The results of each of the above tests are shown in Table 15.

  As is clear from the results shown in Table 15, Comparative Examples 7 and 8 in which the carboxyl group-containing photosensitive resin was used as the photosensitive component were inferior in crack resistance during heat cycle. In Examples 16 to 20 containing the (meth)acrylate compound, the crack resistance was excellent.

  As described above, the (meth)acrylate compound of the present invention and the curable composition containing the same are excellent in photocurability and/or thermosetting property, and also have moisture absorption resistance and heat resistance under high humidity. Further, since a cured product having excellent flexibility can be obtained, it can be used for various purposes such as resist inks, paints and molding materials.

  Further, in addition to the tetra(meth)acrylate compound (B) of the present invention, an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C), a diluting solvent (D), and two per molecule. The curable composition containing the compound (E) having the above cyclic ether, the curing catalyst (F), etc. is excellent in photocurability and/or thermosetting property, and cures even when exposed to high and low temperatures. Since there is no occurrence of cracks in the film and a cured product with excellent properties as described above can be obtained, solder resist, etching resist, plating resist for printed wiring boards, interlayer insulation layers for multilayer wiring boards. It is useful for applications such as permanent masks used in the manufacture of tape carrier packages, resists for flexible wiring boards, resists for color filters, dry films of the above resists, and ink jet printing of the above resists.

Claims (17)

A tetra(meth)acrylate compound represented by the following general formula (1).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group, and X represents a dicarboxylic acid residue.) The tetra(meth)acrylate compound according to claim 1, wherein the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue. The tetra(meth)acrylate compound according to claim 1, wherein the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue represented by any of the following formulas (B1) to (B7).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group.) A cured product of the tetra(meth)acrylate compound according to any one of claims 1 to 3. A curable composition comprising a tetra(meth)acrylate compound represented by the following general formula (1).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group, and X represents a dicarboxylic acid residue.) The curable composition according to claim 5, wherein the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue. The curable composition according to claim 5, wherein the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue represented by any of the following formulas (B1) to (B7).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group.) The curable composition according to any one of claims 5 to 7, further containing another radically polymerizable monomer and/or a polymerization initiator. A cured product of the curable composition according to any one of claims 5 to 8. The cured product according to claim 9, which contains a fiber reinforcing material. (A) a carboxyl group-containing compound, (B) a tetra(meth)acrylate compound represented by the following general formula (1), (C) a polymerization initiator, and (D) a curability characterized by containing a diluting solvent Composition.

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group, and X represents a dicarboxylic acid residue.) The curable composition according to claim 11, wherein the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue. The curable composition according to claim 11, wherein the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue represented by any of the following formulas (B1) to (B7).

(However, R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom or a methyl group.) The curable composition according to any one of claims 11 to 13, further comprising (E) a compound having two or more cyclic ethers in one molecule. The curable composition according to any one of claims 11 to 14, which further contains (F) a curing catalyst. The curable composition according to any one of claims 11 to 15, further comprising (G) another radically polymerizable monomer. A cured product of the curable composition according to any one of claims 11 to 16.

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