WO2005044777A1

WO2005044777A1 - Tetra(meth)acrylate compound, curing composition containing same, and cured products of those

Info

Publication number: WO2005044777A1
Application number: PCT/JP2004/016419
Authority: WO
Inventors: Noboru Kohiyama
Original assignee: Taiyo Ink Manufacturing Co., Ltd.
Priority date: 2003-11-07
Filing date: 2004-11-05
Publication date: 2005-05-19
Also published as: TW200526752A; JPWO2005044777A1

Abstract

A (meth)acrylate compound represented by the formula (1) below and a curing composition containing such a (meth)acrylate compound can be used in various applications such as resist inks, coating materials and molding materials. A curing composition which contains, in addition to the tetra(meth)acrylate compound (B), an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C), a diluent solvent (D), a compound (E) having two or more cyclic ethers in a molecule, a curing catalyst (F) and the like is useful for solder resists for printed circuit boards, etching resists, plating resists, interlayer insulating layers for multilayer wiring boards, permanent masks used in production of tape carrier packages, resists for color filters and the like. (In the formula, R1, R2, R3 and R4 respectively represent a hydrogen atom or a methyl group; and X represents a dicarboxylic acid residue, preferably represents an aliphatic dicarboxylic acid residue or aromatic dicarboxylic acid residue.)

Description

Specification

Tetra (meth) atalylate compounds, curable compositions containing them, and their cured products ''

Technical field

TECHNICAL FIELD [0001] The present invention relates to a novel tetra (meth) atalylate compound, a curable composition containing the same, and a cured product thereof, and is used for various applications such as resist inks, paints, and molding materials. It can be used in some way.

[0002] Further, the present invention relates to a curable composition used for the production of printed wiring boards and the like, and more particularly, to crack resistance due to heat cycling, excellent electrical insulation, and PCT (Brayer 'Tucker Test) The present invention also relates to a curable composition that provides a cured product having excellent properties such as resistance, adhesion, solder heat resistance, chemical resistance, and electroless plating resistance, and a cured product thereof. Height

[0003] In recent years, in the field of aerospace industry and the field of electronic materials, curable compositions containing (meth) acrylate compounds having excellent reactivity and processability have been widely used. In particular, in the manufacture of composite materials used in the aerospace industry, (meth) acrylate compounds, polymerization initiators, and fiber reinforcing materials such as carbon fiber, glass fiber, and aramide fiber In order to obtain not only the photocurability and / or thermosetting properties of the composition, but also the moisture absorption resistance of the cured product and the heat resistance and flexibility under high humidity, the composition must be used in a large amount. The (meta) atalay toy dani is an important 'component.

[0004] However, a composite material obtained by using a curable composition containing a conventional (meta) atalylate ligated product can satisfy both the heat characteristics and flexibility under high humidity. It is not possible to meet the demand for higher performance. That is, a composite material obtained by using a curable composition containing a commercially available (meth) atalylate conjugate had poor thermal and mechanical long-term reliability due to moisture. Such long-term reliability problems are undesirable in other fields, such as the electronic materials field, which is not limited to the aerospace field. [0005] In general, electronic materials such as resist materials for printed wiring boards, particularly cured films of curable compositions used as solder resists, have excellent electrical insulation properties and a PCT (pressure "tucker" test). ) Excellent properties such as resistance, adhesion, solder heat resistance, chemical resistance, and electroless plating resistance are required.

[0006] In particular, recently, since printed wiring boards mounted on automobiles are exposed to high and low temperatures for a long period of time, in addition to the above-mentioned various properties, excellent resistance to cracking due to heat cycles is required. It became so. Powerful properties are not limited to solder resists on printed wiring boards, but are also required for products for other uses such as interlayer insulating layers in build-up multilayer wiring boards. '

[0007] However, a solder resist formed using a curable composition containing a conventional (meth) atalylate compound has to satisfy both the crack resistance due to a heat cycle and the above-mentioned properties. The reality is that you can't.

[0008] To solve the above problems, various (meth) atalylate compounds have been newly developed so far, but they have properties of moisture absorption resistance, heat resistance under high humidity and flexibility. At present, there is still no way to fully satisfy the requirements. For example, a (meth) atalylate toy conjugate obtained by reacting a secondary alcoholic hydroxyl group of a bisphenol type epoxy (meth) acrylate resin with a salty acryloyl group (Japanese Patent Application Laid-Open No. H9-191) can be mentioned. 124714). However, such a (meth) atalyreitic compound is still insufficient to satisfy both excellent moisture absorption resistance and heat resistance under high humidity. On the other hand, di- (meth) atalylate compounds obtained by reacting terephthalic acid chloride with hydroxybutyl (meth) atalylate have been disclosed as (meth) atalylate 'compounds having low hygroscopicity (Japanese Unexamined Patent Publication (KOKAI) 2003—2919). However, since this (meth) acrylate ester has two unsaturated groups in one molecule, it has poor photocuring and / or thermosetting properties, resulting in poor heat resistance under high humidity. There is a problem. On the other hand, as a (meth) atalyl conjugate having excellent photocurability and Z or heat curability, a hexa (meth) obtained by reacting terephthalic acid chloride with pentaerythritol tri (meth) atalylate is preferred. Attalay toy swords (see JP-A-65-252547). However, because this (meth) acrylate compound has six unsaturated groups in one molecule, it is excellent in photocurability and Z or thermosetting properties, but it becomes highly crosslinked by curing. Therefore, a hard and brittle cured product is formed. Therefore, the cured product lacks flexibility and may be broken during aging under high humidity.

[0009] Accordingly, an object of the present invention is to provide a hardened product having excellent photocurability and Z or thermosetting properties, and also having excellent moisture absorption resistance, heat resistance under high humidity, and flexibility. It is another object of the present invention to provide a novel tetra (meth) atalylate compound, a curable composition containing the same, and a cured product thereof.

[0010] Another object of the present invention is to have excellent photo-curing and / or thermo-curing properties, as well as excellent crack resistance due to heat cycles, electrical insulation, PCT (pressure 'cooking force. Test) resistance, An object of the present invention is to provide a curable composition that provides a cured product that sufficiently satisfies various properties such as adhesion, solder heat resistance, chemical resistance, and electroless plating resistance, and a cured product thereof. Disclosure of the invention

[0011] In order to achieve the above object, according to the present invention, a tetracarboxylic acid represented by the following general formula (1)

A (meth) atare toy dagger is provided.

[Chemical 1]

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

[0012] In this specification, (meth) acrylate is a general term for acrylate and methacrylate. Similarly, acrylic acid or methacrylic acid is referred to as (meth) acrylic acid, and acryloyl or methacryloyl. The group is referred to as a (meth) atalyloyl 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 represented by the following formula:

Replacement form (parent rules) The aromatic dicarboxylic acid residues represented by (Bl) to (B7) are more preferably the aromatic dicarboxylic acid residues represented by the following formula (B3).

[Formula 2]

[0014] Further, according to the present invention, there is provided a hardened product of the above-mentioned compound of tetra (meth) acrylate.

[0015] The tetra (meth) acrylate derivatized product of the present invention has four unsaturated groups in one molecule and a pair of units each having a (meth) atalyloyl group at a forked terminal, It has a structure linked by an alkylene, a polymethylene, an aromatic ring, or the like via a thermally stable ester bond or an ester bond. The material is excellent in moisture absorption resistance, heat resistance under high humidity and flexibility.

[0016] According to another aspect of the present invention, there is provided a curable composition comprising the tetra (meth) atalylate compound represented by the general formula (1). According to a preferred embodiment, a tetra (meth) acrylate conjugate 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, preferably, the dicarboxylic acid residue X is any of the aromatic dicarboxylic acid residues represented by the formulas (B1) to (Β7).

Replacement paper-(mm And more preferably an aromatic dicarboxylic acid residue of the formula (B3).

According to a further preferred embodiment of the curable composition of the present invention, the composition contains, in addition to the above-mentioned tetra (meth) phthalate compound, another radically polymerizable monomer and Z or a polymerization initiator, or Contains fiber reinforcement. '

According to still another aspect of the present invention, there is provided a cured product obtained using the curable composition. According to a preferred embodiment, the cured product contains a fiber reinforcement such as glass fiber, carbon fiber, and aramide fiber.

[0019] The curable composition contains a tetra (meth) atalylate compound having the above-mentioned structure, so that the curable composition is excellent in photocurability and / or heat curability, and the cured product has the same moisture absorption resistance. Excellent heat resistance and flexibility under high humidity.

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

According to a further preferred embodiment of the curable composition of the present invention, in addition to the components described above, (E) a compound having two or more cyclic ethers in a molecule, or F) The curing catalyst, some resins further contain (G) other radically polymerizable monomers.

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

[0023] The curable composition comprises (B) tetra (meth) having the above-mentioned structure together with an alkali-soluble (A) compound containing a propyloxyl group, (C) a polymerization initiator, and (D) a diluting solvent. Since it contains an atalylate compound, it can be alkali-developed and has excellent photo-curing and / or thermo-curing properties, and the cured product has excellent resistance to cracks due to heat cycles, electrical insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, electroless gold plating Excellent in properties such as resistance. In addition, 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 each of the above components, the thermosetting after exposure and development causes an electric Various properties such as insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, and electroless plating resistance can be further improved.Furthermore, by including (F) a curing catalyst, the curing start temperature can be reduced. It can lower the temperature and accelerate the thermosetting reaction. In the case of a curable composition containing (G) another radical polymerizable monomer, the photocurability is further improved.

Brief Description of Drawings

FIG. 1 is a graph showing an infrared absorption spectrum of a tetra (meth) atalylate compound obtained in Synthesis Example 1. '

FIG. 2 is a graph showing a nuclear magnetic resonance spectrum of the tetra (meth) atalylate compound obtained in Synthesis Example 1.

FIG. 3 is a graph showing a chromatogram of the tetra (meth) atalylate compound obtained in Synthesis Example 1 by high performance liquid chromatography. ·

FIG. 4 is a graph showing an infrared absorption spectrum of a tetra (meth) T acrylate compound obtained in Synthesis Example 2.

FIG. 5 is a graph showing a nuclear magnetic resonance spectrum of a tetra (meth) atalylate compound obtained in Synthesis Example 2.

FIG. 6 is a graph showing a chromatogram of the tetra (meth) atalylate toyori product obtained in Synthesis Example 2 by high performance liquid chromatography.

FIG. 7 is a graph for explaining a method for obtaining a heat resistant temperature from a TG curve.

FIG. 8 is a graph showing a chromatogram of the oil obtained in Synthesis Example 3 by high performance liquid chromatography.

FIG. 9 is a graph showing an infrared absorption spectrum of the tetra (meth) acrylate conjugate obtained in Synthesis Example 3.

FIG. 10 is a graph showing a nuclear magnetic resonance spectrum of a tetra (meth) atalylate toyid product obtained in Synthesis Example 3.

[FIG. 11] High performance liquid chromatography of the tetra (meth) atalylate compound obtained in Synthesis Example 3 1 is a graph showing a chromatogram according to Example 1.

FIG. 12 is a graph showing a chromatogram of the oil obtained in Synthesis Example 4 by high performance liquid chromatography. ''

FIG. 13 is a graph showing an infrared absorption spectrum of the tetra (meth) acrylate derivative obtained in Synthesis Example 4.

FIG. 14 is a graph showing a nuclear magnetic resonance spectrum of the tetra (meth) atalylate compound obtained in Synthesis Example 4.

FIG. 15 is a graph showing a chromatogram of the obtained tetra (meth) atalylate toyori product obtained by high performance liquid chromatography. .

FIG. 16 is a graph showing an infrared absorption spectrum of the liquid obtained in Synthesis Example 4.

FIG. 17 is a graph showing a magnetic resonance spectrum of the liquid obtained in Synthesis Example 4.

FIG. 18 is a graph showing a chromatogram of the liquid obtained in Synthesis Example 4 by high performance liquid chromatography.

FIG. 19 is a graph showing a chromatogram of the oil obtained in Synthesis Example 5 by high performance liquid chromatography.

FIG. 20 is a graph showing an infrared absorption spectrum of the tetra (meth) atalylate ligated product obtained in Synthesis Example 5. ·

[0044] FIG. 21 is a graph showing a nuclear magnetic resonance spectrum of a tetra (meth) atalylate conjugate obtained in Synthesis Example 5. ¹

FIG. 22 is a graph showing a chromatogram by high performance liquid chromatography of the tetra (meth) acrylate conjugate obtained in Synthesis Example 5.

FIG. 23 is a graph showing a nuclear magnetic resonance spectrum of a mixture of the tetra (meth) atalylate compound obtained in Synthesis Example 6 and 3-attaryloyxy-2-hydroxypropyl methacrylate.

.

FIG. 24 is a graph showing a chromatogram of a mixture of a tetra (meth) acrylate conjugate obtained in Synthesis Example 6 and 3-attaryloyxyx-2-hydroxypropyl methacrylate by high performance liquid chromatography.

[FIG. 25] The tetra (meth) atalylate compound obtained in Synthesis Example 6 and 3-acryloylic acid 4 is a graph showing an infrared absorption spectrum of a mixture with hydroxypropyl methacrylate. · '

FIG. 26 is a graph showing a nuclear magnetic resonance spectrum of 3, -attaryloy xy-2-hydroxypropyl methacrylate.

FIG. 27 is a graph showing a chromatogram of 3-attaryloy oxy-2-hydroxypropyl methacrylate according to high performance liquid chromatography.

FIG. 28 shows a nuclear magnetic resonance spectrum of a monocarboxylic acid having a structure represented by the following formula (3).

This is a graph.

FIG. 29 is a graph showing a nuclear magnetic resonance spectrum of a mixture of the tetra (meth) acrylate conjugate obtained in Synthesis Example 7 and 3-attaryloyoxy2 _′- hydroxypropyl methacrylate.

FIG. 30 is a graph showing a nuclear magnetic resonance spectrum of a mixture of the tetra (meth) atalylate compound obtained in Synthesis Example 8 and 3-attaryloy xy-12-hydroxypropyl methacrylate. ''

[FIG. 31] Chromatography by gel permeation chromatography of a mixture of the tetra (meth) acrylate conjugate obtained in Synthesis Example 8 and 3-acryloyl oxy-1-hydroxypropyl methacrylate

1 is a graph showing grams.

FIG. 32 is a graph showing an infrared absorption spectrum of a mixture of the tetra (meth) acrylate conjugate obtained in Synthesis Example 8 and 3-attaryloyloxy-2-hydroxypropyl methacrylate.

FIG. 33 is a graph showing a chromatogram by gel permeation chromatography of 3-atalylyloxy-2-hydroxypropyl methacrylate.

BEST MODE FOR CARRYING OUT THE INVENTION

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the tetra (meth) atalylate represented by the general formula (1) is excellent in photocurability and / or heat curability. Further, it has been found that the cured product is excellent in moisture absorption resistance, heat resistance under high humidity and flexibility.

Further, the present inventor has proposed a tetra (meth) atalylate toy compound represented by the general formula (1). Curable composition containing, preferably, further curable composition containing other radically polymerizable monomer and Z or a polymerization initiator or further a fiber reinforcing material.Excellent photocurability and / or heat curability. The present invention has been found to give a cured product having excellent moisture absorption resistance and excellent heat resistance and flexibility under high humidity. That is, the tetra (meth) atalylate compound represented by the general formula (1) used in the curable composition of the present invention is

It has a thermally stable ester bond and has four unsaturated groups in one molecule, so it is excellent in photocurability and Z or heat curability, and also excellent in moisture absorption resistance ing. Moreover, since the molecule has an appropriate number of unsaturated groups of four in one molecule, a hardened product having excellent toughness, which hardly forms a hard and brittle hardened film, can be obtained. Therefore, the curable composition containing the radical polymerization polymerizable monomer, the polymerization initiator, the fiber reinforcing material, and the like, together with the tetra (meth) acrylate conjugate, has excellent photocurability and / or excellent curability. A cured product that shows thermosetting properties and has excellent moisture absorption resistance and excellent heat resistance and flexibility under high humidity. [0059] Further, the present inventors have proposed the tetra (meth) atari represented by the general formula (1) together with the carboxyl group-containing conjugate (A), the polymerization initiator (C), the diluting solvent (D) and the like. The curable composition containing the rate compound (B) exhibits excellent photo-curing and / or thermo-curing properties, and the cured product has the above-mentioned electrical insulating properties and PCT in addition to excellent crack resistance. It gives a cured product with excellent properties such as resistance, adhesion, solder heat resistance, chemical resistance, and electroless plating resistance.

[0060] That is, as the curable component, the tetra (meth) acrylate as described above is excellent in light curability and / or heat curability, excellent in water resistance, and gives a cured product excellent in toughness. It contains a tallylate compound (B), an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C) and a diluting solvent (D), and preferably contains two or more per molecule. The curable composition containing the compound (E) having a cyclic ether, the curing catalyst (F), or further another radically polymerizable monomer (G) is excellent in alkali developability and excellent in alkali development. It shows photo-curing and / or thermo-curing properties, and its cured product is necessary for obtaining the above-mentioned properties by the above-mentioned tetra (meth) acrylate compound (B). And heat resistance.

[0061] Hereinafter, the tetra (meth) acrylate conjugate of the present invention, a curable composition containing the same, and ぴ These cured products will be described in detail.

[0062] First, the tetra (meth) atalylate conjugate of the present invention can be obtained by various methods. For example, esterification of 3- (meth) acryloyl oxy-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. is there. Among them, preferred methods include a dehydrochlorination reaction of 3- (meth) atalyloic oxy-2-hydroxypropyl (meth) atalylate with lunar aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride, and 3- ( This is an esterification by a dehydration condensation reaction between a (meth) ataryloy xy-2-hydroxypropyl (meth) atalylate and an aliphatic dicarbonic acid.

[Formula 3]

R ¹ 0 OR ²

CH, = C-C -O-CH, -CH -CH, -1 0— C— C = CH, (2)

OH

(However, RR ² represents a hydrogen atom or a methyl group.)

[0063] The above-mentioned 3 (meth) ataryloy oxy-2-hydroxypropyl (meth) acrylate is a compound that can be obtained by the reaction between (meth) acrylic acid and glycidyl (meth) atalylate. It can also be obtained by the reaction of acid and / or its esters with glycerin and the reaction of (meth) acrylic acid with glycidol.

Examples of the aliphatic dicarboxylic acid chloride include saturated aliphatic 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. And aliphatic unsaturated dicarboxylic acid halides.

[0065] Examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; Examples include aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and examples of aliphatic dicarboxylic anhydrides include succinic anhydride and dartaric anhydride.

Replacement form (Rule 26) Anhydrides of aliphatic saturated dicarboxylic acids, anhydrides of aliphatic unsaturated dicarboxylic acids such as maleic anhydride, and the like. .

Further, as the aliphatic dicarboxylic acid ester, for example, aliphatic saturated dicarboxylic acid esters such as dimethyl malonate, dimethyl succinate, dimethyl gnoletate, dimethyl adipate, dimethyl suberate and dimethyl sebacate; And aliphatic unsaturated dicarboxylic acid esters such as dimethyl maleate.

[0067] Examples of the aromatic dicarboxylic acid chloride include o-phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride and the like.

[0068] Examples of the aromatic dicarboxylic acid include o, -phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,7-naphthalenedirubonic acid and the like; and aromatic dicarboxylic anhydrides such as phthalic anhydride.

[0069] Examples of the aromatic dicarboxylic acid esters include dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylic acid.

[0070] Among these aromatic dicarboxylic acid chlorides, aromatic dicarboxylic acids or anhydrides, and aromatic dicarboxylic acid esters, aromatic dicarboxylic acid chlorides, particularly terephthalic acid, are preferred from the viewpoints of reaction yield, availability, and the like. Chloride and naphthalenedicarboxylic acid chloride are preferred. '

[0071] The esterification reaction of aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride with 3- (meth) ataliyloxy-2-hydroxypropyl (meth) acrylate is carried out by 3- (meth) ataryloyxoxy-2-hydroxy. The propyl (meth) atalylate and the aliphatic dicarboxylic acid chloride or the aromatic dicarboxylic acid chloride may be placed in a reaction vessel, and the reaction may be carried out in advance. Hydroxypropyl (meth) acrylate may be placed in a reaction vessel, and aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride may be added dropwise. Alternatively, aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid chloride may be added. The dicarboxylic acid chloride is placed in the reaction vessel in advance, and the 3- (meth) ataryloy Kishipuropinore (meth) may be performed by adding the Atari rate.

[0072] 3 -— (Meth) Atalilloyl Mouth 2-Hydroxypropyl (Meth) Atalylate and Aliphatic Dical It blending ratio of the carbon acid chloride (charge ratio) is usually 'in a molar ratio ₃ one (meth) Atariroi proxy _ 2-hydroxypropyl (meth) Atari rate Z aliphatic dicarboxylic acid chloride = 4/3 or more On the other hand, the mixing ratio (preparation ratio) with the aromatic dicarboxylic acid chloride is usually 3-(meth) atalyloyloxy- 1-2-hydroxypropyl (meth) atalylate It is desirable that the acid chloride is 4 to 3 or more, more preferably 2 to 1 or more. The use of 3- (meth) ataryloy xylate with a small proportion of 2-hydroxypropyl (meth) acrylate and the formation of desired products other than tetra (meth) acrylate such as di (meth) acrylate And yield decreases. Conversely, if the proportion of 3_ (meth) ataryloy oxy-2-hydroxypropyl (meth) acrylate is too high, a polymerization reaction of unsaturated groups is liable to occur, which is not preferable because of the possibility of polymerization. Also, if the proportion of 3_ (meth) acryloyl oxy-2-hydroxypropyl (meth) acrylate is too high, unreacted 3- (meth) atalylo xy 2 -hydroxypropinole (meth) acrylate will remain. However, it is not economically favorable. Accordingly, the molar ratio of 3- (meth) ataryloy xy-2-hydroxypropyl (meth) atarylate to aliphatic dicarboxylic acid chloride is 3- (meth) acrylic oxy-2-hydroxypropyl (meth) in molar ratio. Atarilet Z aliphatic dicarboxylic acid chloride is preferably from 4 to 3/1, while the proportion with aromatic dicarboxylic acid chloride is 3-(meth) attaryloic acid chloride by molar ratio. It is desirable that hydroxypropyl (meth) acrylate / aromatic dicarboxylic acid chloride = 4Z3 to 3/1, more preferably 2/1 to 3/1. The above mixing ratio is the same even 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. is there.

The reaction temperature in the esterification reaction of 3- (meth) ataryloy xy-2-hydroxypropyl (meth) atalylate with aliphatic dicarbonic acid chloride is from 70 to 150 ° C, preferably from 30 to 120 ° C. ° C, and the reaction can be performed under reduced pressure, normal pressure, or increased pressure. On the other hand, the reaction temperature in the esterification reaction of 3- (meth) ataryloy xy-2-hydroxypropyl (meth) atalylate with aromatic dicarboxylic acid chloride is 0 to 150 ° C, preferably room temperature to 120 ° C. Yes, the reaction can be carried out under reduced pressure, normal pressure, or increased pressure. 1

[0074] 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 dimethyl ether, tetrahydrofuran,, and dioxane; and aliphatic hydrocarbons such as _n -heptane, cyclohexane, and _n- hexane. Hydrogens, nitrogen compounds such as formamide, N, N-dimethylformamide and the like are preferably used. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. However, the amount of 3- (meth) atalyloic oxy-2-hydroxypropyl (meth) atalylate and aliphatic dicarboxylic acid chloride or aromatic dicarboxylic acid. For a total of 100 parts by mass, the range of 50 to: L000 parts by mass is preferable. The reaction temperature and the amount of the solvent used are determined when aliphatic dicarboxylic acid or its anhydride or aliphatic dicarboxylic acid ester, or aromatic dicarboxylic acid or its anhydride or aromatic dicarboxylic acid ester is used. The same applies to

[0075] The esterification reaction is preferably performed in the presence of a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, 4-methoxyphenol, 4-tert-butylcatechol, and the like are suitably used. These polymerization inhibitors can be used alone or in combination of two or more. The amount of the polymerization inhibitor to be used is usually within the range of 0.0015 parts by mass with respect to 100 parts by mass of 3- (meth) a.cryloyl xy-2-hydroxypropyl (meth) atalylate. . The amount of the polymerization inhibitor to be used is not limited to the case where aliphatic dicarboxylic acid or its anhydride or aliphatic dicarboxylic acid ester, or aromatic dicarboxylic acid or its anhydride or aromatic dicarboxylic acid ester is used. The same is true. .

Further, tertiary amines such as trimethylamine, triethylamine, 4-dimethylaminopyridine and the like are appropriately used in order to capture hydrogen chloride generated at the time of esterification. These tertiary amines can capture hydrogen chloride by forming quaternary ammonium salts with hydrogen chloride. These tertiary amines can be used alone or in combination of two or more.

When aromatic dicarboxylic acid chloride, aromatic dicarboxylic acid or its anhydride, or aromatic dicarboxylic acid ester is used, after the esterification reaction is completed, triethylamine is added. W 200

After dissolving a basic salt of an amine such as 14 in water, an extraction solvent such as ethyl acetate or methylene chloride is added to extract a reaction mixture containing the tetra (meth) atalylate 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 a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, or the like. Furthermore, 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 solution of sodium hydrogen carbonate.

On the other hand, there are aliphatic dicarboxylic acids or their anhydrides or aliphatic dicarboxylic acid esters, and! / Is an aromatic dicarboxylic acid or its anhydride or aromatic dicarboxylic acid ester. And 3- (meth) acryloylic acid ester The esterification reaction with 2-hydroxypropyl (meth) acrylate is usually carried out with aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as getyl ether, tetrahydrofuran and dioxane, n-heptane and cyclohexane. Kisa

Esterification of sulfuric acid, hydrochloric acid, phosphoric acid, fluoridated boron, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin, etc. in organic solvents such as aliphatic hydrocarbons such as The reaction is carried out using a catalyst in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, 4-methoxyphenol and 4-tert-butylcatechol. -

The above esterification reaction is carried out in an aromatic hydrocarbon such as benzene, toluene and xylene, an ether such as getyl ether, tetrahydrofuran and dioxane, and a fat such as n-heptane., Cyclohexane and n-xane. Condensation agents such as dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in organic solvents such as aromatic hydrocarbons, nitrogen compounds such as formamide and N, N-dimethylformamide Tertiary amines such as trimethylamine, triethylamine, 4-dimethylaminopyridine, and the like, using hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, Pheno thiazine, 4-methoxypheno Le, can also be carried out in the presence of a polymerization inhibitor such as 4-tertiary butyl catechol.

[0080] The tetra (meth) atalylate compound of the present invention can be used as a reactive diluent and can impart flexibility. For this purpose, 3- (meth) atalyloyloxy_2-hydroxypropyl (meth) atalylate represented by the general formula (2) can be mixed. The mixing amount is sufficient at 70 parts by mass or less, preferably at 50 parts by mass or less, based on 100 parts by mass of the tetra (meth) acrylate ester compound. It is not preferable that the mixing amount of the di (meth) atalylate compound is more than 70 parts by mass because the heat resistance of the tetra (meth) atalylate compound may be reduced. , '

[0081] The tetra (meth) atalylate compound of the present invention can be rapidly produced by irradiation with active energy rays and / or heating in the presence of a polymerization initiator (photoradical polymerization initiator, thermal radical polymerization initiator). In addition to radical polymerization, it can be cured by simply heating, and can also be cured by X-ray or electron beam irradiation.

[0082] Further, the tetra (meth) atalylate toy conjugate of the present invention is useful as a resin matrix of a composite material (fiber reinforced plastic). Therefore, the tiger (meta) atalylate toy compound of the present invention is excellent in photo-curability and Z or thermo-curability as described above, and the cured product has moisture absorption resistance and heat resistance under high humidity. Due to its properties of excellent flexibility and flexibility, it is extremely useful as a composite material (fiber reinforced plastic), especially in the aerospace industry, but as a curable component in various resist materials and paints for printed wiring boards. Can also be used advantageously.

[0083] First, a curable composition containing the tetra (meth) atalylate compound represented by the general formula (1), in particular, other radically polymerizable monomers and Z or a polymerization initiator, or further fiber reinforced. The curable composition containing materials and the like will be described.

[0084] Examples of the radical polymerizable monomer include styrene derivatives such as styrene and divinylbenzene; 2-hydroxyethyl (meth) atalylate, 2-hydroxypropyl (meth) atalylate, and 3- (meth) atalyloyl. Xy 2-hydroxypropyl (meth) acrylate, hydroxyl-containing atalylates such as pentaerythritol triatalylate and dipentaerythritol pentaatalylate; water-soluble such as polyethylene glycol diatalylate and polypropylene glycol diatalylate Polymethyl alcohol acrylates such as trimethylolpropane triatalylate, pentaerythritol tetraatalylate, dipentaerythritol hexaatalylate, etc .; Lopan, hydrogenated Polyfunctional alcohols such as bisphenol A or polyhydric phenols such as bisphenol A and biphenol: acrylates of ethylene oxide adducts and / or propylene oxide adducts; polyisocyanates which are modified isocyanates of the hydroxyl group-containing acrylates Functional or monofunctional polyurethane acrylates; epoxy acrylates which are (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidinole ether or phenol nopolak epoxy resin, and Methacrylates corresponding to the above acrylates, or di (meth) acrylate conjugates described in JP-A-2003-2919, tetra (meth) atalylate compounds described in JP-A-9-124714, Hexa (meta) atarile described in No. 62-5252 Toys 匕合 product and the like, which alone or may be used two or more kinds. The purpose of using these radically polymerizable monomers is to increase the photocurability and the heat or curability of the composition. The radically polymerizable monomer which is liquid at room temperature serves not only to increase the photocurability and / or the thermosetting property of the composition, but also to adjust the composition to a viscosity suitable for various coating methods. The amount of these radically polymerizable monomers can be arbitrarily determined according to the purpose of use and the desired physical properties. Usually, however, 100 parts by mass of the above-mentioned tetra (meth) acrylate is 200 parts by mass or less. Is preferred. '

[0085] The tetra (meth) atalylate compound used in the present invention can be cured by simply heating and can be cured by X-ray or electron beam irradiation. It is preferable to use such a polymerization initiator since radical polymerization is rapidly performed by irradiation with active energy rays and Z or heating in the presence of a photoradical (polymerization initiator, thermal radical polymerization initiator). . ·

[0086] As the polymerization initiator, a photo-radical polymerization initiator and a thermal-radical polymerization initiator as described below can be suitably used, and the compounding amount thereof is 100 parts by mass of the tetra (meth) atalylate compound. (In the case of using the radical polymerizable monomer, the total amount of these is 100 parts by mass.) The amount is preferably 30 parts by mass or less. In the case of a thermal radical polymerization initiator, the ratio is preferably 0.1 to 10 parts by mass.

[0087] Examples of the fiber reinforcing material include glass fiber, carbon fiber, and aramide fiber. ^ These fibers can be used alone or as a mixture of two or more. '' Ratio in the composition of the fiber reinforcement, preferably 10 to 80% by volume, more preferably rather 50-70 volume ^_0/0 turbocharger.

[0088] The curable composition of the present invention includes the above-mentioned 3- (meth) atalyloic oxy-2-hydroxypropyl (meth) atalylate, aliphatic dicarboxylic acid chloride or aliphatic dicarboxylic acid, or It may contain an unreacted monomer at the time of the esterification reaction with an anhydride or an aliphatic dicarboxylic acid ester, or a by-product such as a generated di (meth) atalylate compound or a polymer.

[0089] The curable composition of the present invention may further contain a solvent as described below, if necessary, alone or as a mixture of two or more kinds. The purpose of the solvent is to dissolve the tetra '(meth) atalylate compound, the radical polymerizable monomer, the polymerization initiator and the like, and to adjust the composition to a viscosity suitable for the coating method. The compounding amount of the solvent can be an arbitrary amount according to the coating method.

[0090] The curable composition of the present invention may be mixed with an inorganic thickener as described below to the extent that the properties of the cured product are not degraded. The ratio is sufficient, and for example, the ratio is 0.2 to 20 parts by mass, preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the tetra (meth) atalylate conjugate.

[0091] In the curable composition of the present invention, if necessary, furthermore, for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion, hardness and heat resistance under high humidity, Inorganic fillers and organic fillers described below can be used alone or in combination of two or more. 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 tetra (meth) atalylate toy conjugate.

[0092] The curable composition of the present invention may further comprise a coloring agent, a thermal polymerization inhibitor, an antifoaming agent, a Z or leveling agent, a silane coupling agent, and the like as described below. Such known and commonly used additives can be blended. Furthermore, the curable composition of the present invention may optionally 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 compounding amount of the flame retardant is usually from! To 200 parts by mass, preferably from 5 to 50 parts by mass with respect to 100 parts by mass of the tetra (meth) acrylate compound. 1 o ratio. When the blending amount of the flame retardant is within the above range, the flame retardancy, moisture absorption resistance, heat resistance and flexibility under high humidity of the cured product are highly balanced, which is preferable.

[0093] The tetra (meth) atalylate 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 aerospace industry. This type of composite material is generally obtained by impregnating a fiber-reinforced material, for example, a fiber-reinforced material composed of fibers such as carbon fiber, glass fiber, and aramid fiber (for example, Kepler fiber) with a liquid curable composition. , Followed by curing. The fiber reinforcement used at this time can take various forms, for example, a multi-layer fiber, a two-dimensional sheet, or a three-dimensional or multi-dimensional woven fabric. .

[0094] A curable composition containing another radically polymerizable monomer, a polymerization initiator, an initiator, and a fiber reinforcing material together with the tetra (meth) atalylate ligated product is charged into a mold, or After the fiber and the reinforcing material are put in a mold in advance, the curable composition of the present invention containing no fiber reinforcing material is poured into the mold, and then the mold filled with the composition is added. By heating and curing, a fiber-reinforced plastic can be obtained. Alternatively, a fiber-reinforced plastic can be obtained by curing the composition filled in the mold by irradiation with active energy. 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 nitride lamp, or the like is suitable as a light source for irradiating active energy rays. In addition, laser beams, X-rays, and electron beams can also 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 tetramethyl (meth) acrylate compound (B), an alkali-soluble carboxyl group-containing compound (A), a polymerization initiator (C), and a diluent solvent (D). And preferably further contains, as a thermosetting component, a compound (E) having two or more cyclic ethers in one molecule or a curing catalyst (F), and if necessary, other radical polymerizable components. Contains monomer (G).

First, the carboxyl group-containing compound (A) used in the curable composition is a compound having at least one, preferably two or more carboxyl groups in one molecule. Specifically, a carboxyl group-containing photosensitive material having an ethylenically unsaturated double bond itself. Both resins and resin containing a carboxyl group having an ethylenically unsaturated double bond can be used, and are not limited to specific ones. Oligomers or polymers).

(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 having an unsaturated double bond (b),-

(3) Secondary compound formed by reacting a copolymer of a compound (c) having an epoxy group and an unsaturated double bond with a compound (b) having an unsaturated double bond with an unsaturated carboxylic acid (a). A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with a hydroxyl group of

(4) a copolymer of an acid anhydride having an unsaturated double bond (e) and a compound having an unsaturated double bond (b) is compounded with a compound having a hydroxyl group and an unsaturated double bond (f). Carboxyl group-containing photosensitive resin obtained by the reaction,

(5) The esterification reaction (total esterification or partial esterification) of the epoxy group of the polyfunctional epoxy compound having at least two epoxy groups in one molecule (g) and the carboxyl group of the unsaturated monocarboxylic acid (h) , Preferably all esterification), and a carboxyl group-containing photosensitive resin obtained by further reacting the generated hydroxyl group with a saturated or unsaturated polybasic anhydride (d).

(6) A compound having an unsaturated double bond (b) and a glycidyl (meth) acrylate copolymer have one carboxy group in one molecule in the epoxy group, and have an ethylenically unsaturated bond.

A carboxyl group-containing resin obtained by reacting an organic acid (i) having no carboxyl group, and reacting a generated secondary hydroxyl group with a saturated or unsaturated polybasic anhydride (d),

(7) a carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic anhydride (d) with a hydroxyl group-containing polymer (j),

(8) A compound having an epoxy group and an unsaturated double bond in a carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic anhydride (d) with a hydroxyl group-containing polymer (j). carboxyl group-containing photosensitive resin obtained by further reacting (c),

(9) A polyfunctional epoxy compound having at least two epoxy groups in one potato) (g), an unsaturated monocarboxylic acid (h), at least two hydroxyl groups in a molecule, and an epoxy group. The reaction product (I) with a compound (k) having one other reactive group other than a hydroxyl group

, A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d),

(10) An unsaturated group-containing polycondensate comprising the reaction product of the above reaction product (I), a saturated or unsaturated polybasic anhydride (d), and an unsaturated group-containing monoisocyanate (m). Urethane carboxylate resin,

(11) A polyfunctional oxetane compound (n) having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid (h) to form a primary hydroxyl group in the resulting modified oxetane resin. A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d),

(12) An unsaturated double bond is introduced into the reaction product of the bisepoxy conjugate (p) and the dicarboxylic acid (q), followed by bow I and a saturated or slightly unsaturated polybasic acid anhydride (d) The force obtained by reacting Zolepoxyl group-containing resin,

(13) An unsaturated double bond is introduced into the reaction product of the bisepoxy compound (p) and the bisphenols (r), followed by the reaction with a saturated or unsaturated polybasic anhydride (d). Carboxyl group-containing resin obtained by

(14) The reaction product of the nopolak phenolic resin (s) and the alkylene oxide (t) is reacted with an unsaturated monocarboxylic acid (h), and the obtained reaction product is reacted with a saturated or unsaturated polybasic anhydride. A carboxyl group-containing photosensitive resin obtained by reacting the product (d).

The carboxyl group-containing resin (1) includes 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. The carboxyl group-containing photosensitive resin (2) is a compound (b) having an unsaturated carboxylic acid (a) and an unsaturated double bond (b). )) A copolymer having an ethylenically unsaturated group such as a vinyl group, an aryl group or a (meth) acryloyl group and a reactive group such as an epoxy group or an acid chloride in a part of the carboxyl group of the copolymer A resin, for example, glycidyl (meth) acrylate, and the unsaturated double bond of the compound is introduced into the side chain. A part of the carboxyl group of the unsaturated carboxylic acid (a), which is one of the monomer components of the copolymer, remains unreacted. It is soluble.

The carboxyl group-containing photosensitive resin (3) is a compound (c) having an epoxy group and an unsaturated double bond in the molecule, for example, glycidyl (meth) acrylate, a-methyldaricidyl (meth) Acrylate and the like, and the soil hydroxy group of the copolymer of the compound (b) having an unsaturated double bond are reacted with the carboxyl group of the unsaturated carboxylic acid (a) to form the unsaturated carboxylic acid. In addition to introducing an unsaturated double bond into the side chain, the secondary hydroxyl group generated by the above addition reaction is added to a polybasic anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like. This is a tree in which a carboxyl group was introduced into the side chain by subjecting the compound to an Esterich reaction.

[0100] The carboxyl group-containing photosensitive resin (4) has an unsaturated double bond and an acid anhydride (e) such as maleic anhydride, itaconic anhydride and the like.

'. Compound (f) having a hydroxyl group and an unsaturated double bond in part of the acid anhydride group of the copolymer of compound (b), such as hydroxyalkyl (meth) acrylates and (meth) acrylate A half-ester is obtained by reacting a monomer obtained by reacting carbolactone or a hydroxyl group such as a macromonomer obtained by reacting a polyfunctional prolactone oligomer with (meth) atalylate to form a half-ester.

Is a resin having an unsaturated double bond introduced into the side chain.

[0101] The carboxyl group-containing photosensitive resin of the above (5) includes bisphenol A type, bisphenol F type, bisphenol S type, phenol nopolak type, cresol novolak type, biphenol type, bixylenol type, N —The epoxy group of a known 'conventional epoxidized' compound such as a glycidinole type (g) is reacted with the hydroxyl group of an unsaturated monocarboxylic acid (h) such as (meth) acrylic acid, for example, epoxy epoxide A resin in which a carboxyl group is introduced into a side chain by generating a rate and performing an esterification reaction of the polybasic acid anhydride (d) with the secondary hydroxyl group generated by the above addition reaction.

[0102] The carboxyl group-containing resin (6) has a compound having the unsaturated double bond and no hydroxyl group or acid group, such as alkyl, (meth) acrylate, substituted or unsubstituted styrene. (B) and the glycidyl group of the copolymer having glycidyl (meth) acrylate as the main chain, the organic acid (i) having one carboxyl group per molecule and no ethylenically unsaturated bond ), For example, a resin obtained by reacting an alkyl carboxylic acid having 2 to 17 carbon atoms, an alkyl carboxylic acid having an aromatic group, or the like, and adding the polybasic anhydride (d) to a secondary hydroxyl group produced. is there.

[0103] The carboxyl group-containing resin (7) is a hydroxyl group-containing polymer (j), for example, an olefin-type hydroxyl group-containing polymer, an acrylic polyol, a rubber-based polyol, a polybutyral, a styrenearyl alcohol-based resin, and a cellulose. It is a resin having a carboxyl group introduced by reacting the polybasic acid anhydride (d) having relatively weak acidity.

On the other hand, the carboxy group-containing photosensitive resin (8) is an epoxy resin of the compound (c) having an epoxy group and an unsaturated double bond in the carboxyl group of the carboxyl group-containing resin (7). This is a resin obtained by reacting a group and introducing an unsaturated double bond of the compound (c) into a side chain.

In the synthesis reaction of the carboxyl group-containing photosensitive resin of the above (9), an unsaturated monocarboxylic acid (h) (or a compound (k)) is reacted with a polyfunctional epoxy compound (g), A first method of reacting the compound (k) (or the unsaturated monocarboxylic acid (h)) with the polyfunctional epoxy compound (g), the unsaturated monocarboxylic acid (h) and the compound (k). There is a second method of reacting at the same time. Either method may be used, but the second method is preferable. ■

'A compound having at least two or more hydroxyl groups and one other reactive group other than a hydroxyl group that reacts with an epoxy group (for example, a carboxyl group, a secondary amino group, etc.) in one molecule (k Examples of) include poly.hydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; and dialysates such as diethanolamine and diisopropanolamine. And the like. ,

On the other hand, in the synthesis reaction of the unsaturated group-containing polycarboxylic acid urethane resin of the above (10), the reaction product (I) is reacted with a polybasic acid anhydride (d). It is preferable to react the unsaturated group-containing monoisocyanate (m) with the hydroxyl group in the group-containing polycarboxylic acid resin. [0108] Specific examples of the unsaturated monoisocyanate (m) include, for example, methacryloyl isocyanate, methacryloyloxyshethyl isocyanate, and organic diisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate). Isocyanate, isophorone diisocyanate, hexamethylene diisocyanate) and the above-mentioned (meth) acrylate having one hydroxyl group in one molecule in an approximately equimolar ratio. And the like.

The carboxyl group-containing photosensitive resin of the above (11) has an oxetane ring as a starting material, instead of an epoxy resin which mainly produces a secondary hydroxyl group by reaction with an unsaturated monocarboxylic acid. Using the compound, the polyfunctional oxetane conjugate (n) is reacted with an unsaturated monocarboxylic acid (h), and a polybasic acid anhydride (d) is further added to the primary hydroxyl group of the resulting modified oxetane resin. By the reaction, the binding site is hardly cleaved thermally, and the resin has excellent thermal stability.

[0110] The resin containing a propyloxyl group of the above (12) and (13) is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a brominated bisphenol A type epoxy resin. Resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bisepoxy conjugated product ( _P ) such as bixylenol type epoxy resin, and dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, phthalic acid and isophthalic acid An unsaturated double bond is introduced into the reaction product of the acid (q) or bisphenols (r) such as bisphenol 1/1 / A and bisphenol F, and then the secondary The polybasic acid anhydride (d) is further reacted with hydroxyl groups or remaining hydroxyl groups, etc. to obtain a resin having excellent thermal stability. The introduction of an unsaturated double bond is generally carried out by reacting an ethylenically unsaturated group such as a vinyl group, an aryl group or a (meth) atalyloyl group with a hydroxyl group, a carboxyl group or the like remaining in the above-mentioned reaction and a generated hydroxyl group. The reaction is carried out by reacting a compound having a reactive group such as an epoxy group having an acid group or an acid chloride. .

[0111] The hapoxyl group-containing photosensitive resin of (14) is excellent in flexibility and elongation due to chain extension by addition reaction of alkylene oxide (t) of novolak type phenol resin (s), and Unsaturated monocarboxylic acid () and polybasic anhydride (d) are added to the terminal hydroxyl group generated by the alkylene oxide addition reaction, and the unsaturated group or carboxyl group is present on the same side chain. And at the ends of the side chains, It has excellent alkali developability due to the presence of terminal carboxyl groups apart from the main chain. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like.

[0112] The acid value of the carboxyl group-containing compound (A) as described above is preferably from 20 to 200 mg KOHZg, and more preferably from 50 to 120 mg KOHZg. When the acid value is lower than 20 mg KOHZg, the solubility in an aqueous alkali solution becomes poor, and the development of the formed coating film becomes difficult. On the other hand, if it is higher than 200 mgKOHZg, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable. '

[0113] The above-mentioned carboxyl group-containing compounds (carboxyl group-containing resin and hydroxyl group-containing photosensitive resin) can be used alone or in combination of two or more.

[0114] The mixing ratio of the tetra (meth) atalylate toy conjugate (B) is 5 to 100 parts by mass relative to 100 parts by mass of the carboxyl group-containing compound (A) (solid content, The same is appropriate, and preferably a ratio of 10 to 50 parts by mass. When the compounding ratio of the tetra (meth) ataryl compound (B) is less than 5 parts by mass, it is difficult to obtain sufficient photocurability and Z or thermosetting properties. In addition, the properties of the cured product are not further improved, and the excess amount is economically undesirable.

[0115] The curable composition of the present invention includes the above-mentioned 3_ (meth) atalyloy xy-2-hydroxypropyl (meth) atalylate, aliphatic dicarboxylic acid chloride or aliphatic dicarboxylic acid or anhydride or fat thereof. It may contain an unreacted monomer in the esterification reaction with an aromatic dicarboxylic acid ester or a by-product such as a produced di (meth) acrylate M-conjugate or a polymer.

[0116] The tetra (meth) atalylate toy conjugate used in the present invention can be cured by simply heating, and can also be cured by X-ray or electron beam irradiation, but the polymerization initiator (C ) In the presence of (photo-radical polymerization initiator (C1) and thermal radical polymerization initiator (C2)), radical polymerization is rapidly performed by irradiation with active energy rays and Z or heating. It is preferable to use . 117]. As the photoradical polymerization initiator (C1), known compounds that generate radicals upon irradiation with active energy rays can be used, and specific examples thereof include benzoin, benzoin methyl ether, and benzoin ethyl. Benzoin and benzoin alkyl earth ethers such as ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenones such as acetophenone; 2-methyl-1 _ [4- (methylthio) phenyl] 1 -2-morpholinopropane 1-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane Aminoacetophenones such as 1-one, N, N-dimethylaminoacetophenone; 2-methyla Anthraquinones such as anthraquinone, 2-ethylanthraquinone, 2-t-butyl, anthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2 Thioxanthones such as 4,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triallylimidazole dimer; riboflavin tetrabutylate; 2-mercaptoben Thiol compounds such as zoimidazole, 2-mercaptobenzozoxazole, and 2-mercaptobenzozothiazole; 2,4,6-tris-s-triazine, 2,2,2-triproethanol, and tribromomethylphenylsulfone Organic halogen compounds: benzophenone, 4, 4-bis ( Benzophenones such as (ethylamino) benzodinone or xanthone; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These known and commonly used photoradical polymerization initiators can be used alone or as a mixture of two or more kinds. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino Photoinitiating aids such as tertiary amines such as benzoate, triethylamine and triethanolamine can be added. Also, CGI-784 etc. which absorbs in the visible light region (Ciba 'Specialty Chemicals Co., Ltd. )) Can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Methyl-11- [4- (methylthio) phenyl] _2-morpholinopropane-1-one, 2-benzyl-2-methylamino-1- ( 4-morpholinophenyl) -butane-1-one and the like, but are not particularly limited to these. Not only photopolymerization initiators and photoinitiating auxiliaries, but also those that absorb light in the ultraviolet or visible light range and radically degrade unsaturated groups such as (meth) acryloy / le group Or • Can be used in combination.

Examples of the thermal radical polymerization initiator (C2) include, for example, benzoyl peroxide, coumarin peroxide, di-tert-butyl peroxide, p-menthane peroxide, 2 ′, 5-dimethyl-2,5- Di (t-butylperoxy) hexine-1,3, diisopropylben; organic peroxides such as senhydride peroxide, t_butylperoxy-1,2-ethylhexanoate; 2- (carpamoylazo) isobutyl mouth-tolyl, 2-phenyl Luazo-4-methoxy 2,4-dimethylvaleronitrile, azodi-t-octane, 2,2'-azobisisobutyronitrile, 2,2'-azobis, 2-methylbutyronitrile, 2,2'-azobis-1 2 , 41 divaleronitrile, 1, diazobis (1-acetoxy-11-phenylene), diazobis-1-1-cyclohexanecarbo Azo-based initiators such as nitrile, dimethyl-1,2,2-azobisisobutyrate, 4,4'-azobis-14-cyanobaric acid, 2-methyl-2,2'-azobispropane nitrile No.

[0119] The amount of the polymerization initiator (C) as described above is normally sufficient in a quantitative ratio. However, the photo-radical polymerization initiator is added to 100 parts by mass of the carboxyl group-containing compound (A). In this case, the ratio is preferably 0.5 to 25 parts by mass, and in the case of the thermal radical polymerization initiator, the ratio is preferably 0.110 parts by mass.

[0120] Examples of the diluting solvent (D) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzene; ethylene daryl monoethyl ether; Ethylene glycol monomethyl ether, ethylene glycol monobutynole ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl monoenoate ether, diethylene glycol monoethyl monoenoate ether, propylene glycol monomethyl ether monoethylene Glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol ethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, and ethylene glycol monoethyl ether acetate; ^ Ethylene glycol / lemonobutynoleate enorea acetate, dimethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Acetates such as propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether And petroleum-based solvents such as petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more. The purpose of using these diluting solvents is to dissolve the carboxyl group-containing compound (A) and the like, and to adjust the composition godly suitable for the coating method. The compounding amount of the diluting solvent (D) can be an arbitrary amount according to the coating method.

Examples of the compound having two or more cyclic ethers in one molecule) include oxsilane compounds, oxetane compounds, oxolani conjugates, and the like.

Examples of the oxysilane compounds include, for example, Epikote 828, Epikote 834, Kopicoat 1001, Epikote 1004, and Epicron 840, Epicron 850, and Epicron 1050, Epicron, manufactured by Dainippon Ink and Daikaku Kogyo Co., Ltd. manufactured by Japan Epoxy Resins Co., Ltd. 2055, YD_011, YD-013, YD-127, YD-128, manufactured by Toto Kasei Co., Ltd., DER 317, DER 331, DER 661, DER 664, manufactured by Dow Chemical Co., Ltd., Sumitomo Corporation Bisphenol A type epoxy resin such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names) manufactured by Epoxy Coat YL903, manufactured by Japan Epoxy Resin Co., Ltd. Epiclon 152 and Epiclon 165 manufactured by Nippon Ink Chemical Industry Co., Ltd., Epototo YDB-400 and YDB-500 manufactured by Toto Kasei Co., Ltd. D.'ER 542 manufactured by Dow Chemical Co., Ltd., Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESB Brominated epoxy resins such as 400, ESB-700 (both are trade names); Epikote 1 52, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN 431, DEN 438 manufactured by Dow Chemical Co., Ltd., Dainippon Ink & Chemicals, Inc. Epiclone N-730, Epiclone N-770, Epiclone N_865, manufactured by Industrial Co., Ltd., Epototo YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd., EPPN-201, EOCN manufactured by Nippon Kayaku Co., Ltd. -Novolak type epoxy resin such as 1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220 (all trade names); Epiclon 830 manufactured by Ink Chemical Industry Co., Ltd., Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YDF-170 manufactured by Toto Kasei Co., Ltd. Bisphenol F-type epoxy resin such as YDF-175, YDF-2004 (all trade names); Epototo ST-2004, ST-2007, ST-3000 (all trade names) manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A-type epoxy resin; Epikoto 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotote YH-434 manufactured by Toto Kasei Co., Ltd., and Sumiepoxy ELM manufactured by Sumitomo Iridaku Kogyo Co., Ltd. — Glycidylamine-type epoxy resin such as 120 (all trade names); Alicyclic epoxy resin such as Celloxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; YL—933 manufactured by Japan Epoxy Resin Co., Ltd. Nippon Kayaku Co., Ltd. EPPN-501, EPH-502 (all trade names) and other trihydroxy fuel methane type epoxy resins; Japan Epoxy Resin Co., Ltd. YL-6056, ΎΧ-4000 Or YL-6121 (both ^ product names) Biphenol-type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denshi Co., Ltd., EXA-1514 manufactured by Dainippon Ink and Chemicals, Inc. bisphenol S type epoxy resin trade name); Japanepoki Shirejin Co. Ltd. Epikoto 15 ⁷ S (trade name) bisphenol a novolac type such Epoki shea resin; manufactured by Japan epoxy resins Co. of Co. Epikoto YL- 931 (trade name) or other tetraphenylolethane-type epoxy resin; Nissan Chemical Industries, Ltd. TEPIC (trade name) or other complex cyclic epoxy resin; NOF Corporation's Bremma ^ DGT (trade name) ), Etc .; Tetraglycidyl xylenylethane resin such as ZX-1063 (trade name) manufactured by Toto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., Dainippon Ink and Chemicals ( HP-4032, Naphthalene group-containing epoxy resin such as EXA-4750 and EXA-4700 (all trade names); dicyclopentadiene such as HP-7200, HP-7200H (all trade names) manufactured by Dainippon Ink and Chemicals, Inc. Epoxy resins having a skeleton; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M (both trade names) manufactured by Nippon Oil & Fats Co., Ltd .; and hydantoin-type epoxy resins, cyclohexylmale Epoxy halohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene with bisphenol A type epoxy resin. And functional epoxy resins (International Publication WO 01,024774).

Examples of oxetanei conjugates include, for example, 3,7-bis (3-oxetanyl) -1-5-oxa Nonane, 3, 3 '-(1,3- (2-methylenyl) propanedylbis (oxymethylene)) bis- ( _3- ethylethyloxetane), 1,4_bis [(3-ethylethyl-3-oxetanylmethoxy) [Methyl] benzene, 1,2-bis [(3-ethyl-13-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol 'Ethyl bis (3-ethyl-13-oxetanylmethyl) ether, dicyclopentylbis (3-ethynole-3-oxetane-methyl) ether, triethylene glycol bis (3-ethynole-3-oxetanalmethyl) Ether, tetraethylene dalicol bis (3-ethyl-13-oxetanylmethyl) ether, tricyclodecanedidimethylmethylene (31-ethyl-13-oxetanylmethyl) ether, Methylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl_3-oxetanylmethoxy) butane, 1,6_bis (3-ethyl-13-oxetanyl) Methoxy) hexane, pentaerythritol norethris (3-ethyl-13-oxetanylmethyl) ether, pentaerythritol noretetrakis (3-ethyl-13-oxetanylmethyl) ether and the like.

The compound (E) having two or more cyclic ethers in one molecule described above can be used alone or in combination of two or more. These compounds having a cyclic ether can be cured by heat to improve properties such as resist adhesion and heat resistance. The amount of the compound is 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing compound (A), and is preferably 15 to 60 parts by mass. If the compounding amount of the cyclic ester-containing compound (E) is less than the above range, the hygroscopicity of the cured film becomes high and the PCT resistance tends to decrease, or the solder heat resistance and electroless plating resistance Is also low. On the other hand, if it exceeds the above range, the developability of the coating film and the electroless plating resistance of the cured film become poor, and the PCT resistance also becomes poor.

As the curing catalyst (F), for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2_phenylimidazole, 4-phenylimidazole, 1 -Imidazole derivatives such as cyanoethyl- 1- 2-phenyleimidazole, 11- (2-cyanoethyl) -2-ethyl-4-methyl imidazole; dicyandiamide, benzyldimethylamido, 4- (dimethylamino) -N, N-dimethyl Benzylamine, 4-methoxy-N, N-dimethylbenzinoleamine, 4-methyl-N, N-dimethylbenzamine Amine conjugates such as benzylamine; hydrazine conjugates such as adipic hydrazide and sebacic hydrazide; and phosphorus conjugates such as triphenylphosphine can be used. Examples of commercially available products include 2MZ-A, 2MZ_〇K, 2PHZ, 2P4BHZ, and 2P4MHZ (all of which are trade names of imidazole compounds) manufactured by Shikoku Chemicals Co., Ltd .; —CAT3503N, U— CAT3502T (trade name of block isocyanate compound of dimethylamine), DBU, DBN, U—CATSA102, U—CAT5002 (bicyclic amidine compound and its salt) And the like. In particular, if the purpose is to improve the thermosetting properties, the present invention is not limited to these, and any other catalyst may be used as long as it accelerates the reaction between a compound having a cyclic ether and a compound having a cyclic ether and a carboxylic acid. It does not work even if used alone or as a mixture of two or more. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-16-methacryloyloxexetil_S-triazine, 2-vinyl-4,6-diamino-1S—which also functions as an adhesion promoter S-triazines, such as triazine, 2-butyl-1,4,6-dianmino S-triazine 'isocyanuric acid adduct, 2,4-diamino-16_metararyloyloxetyl-1-S-triazine / isocyanuric acid adduct Derivatives can be used, and these compounds are preferably used in combination with the curing catalyst. The amount of the curing catalyst to be blended in a usual quantitative ratio is sufficient, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass, based on 100 parts by mass of the carboxyl group-containing compound (containing). Parts.

Examples of the radical polymerizable monomer (G) include 2-hydroxyethyl (meth) acrylate, '2-hydroxypropyl (meth) acrylate, pentaerythritol triatalylate, and dipentaerythritol pentaatalylate. Hydroxyl-containing atalylates; water-soluble atalylates such as polyethylene glycol diatalylate and polypropylene glycol diatalylate; trimethylolpropane triatalylate, pentaerythritol tetraacrylate, dipentaerythritol hexatalylate, etc. Polyfunctional alcohol acrylates of polyhydric alcohols; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyphenols such as bisphenol A and biphenol Atari rate such Id adduct and / or propylene oxide adducts; polyfunctional or monofunctional polyurethane § click a Isoshianeto modified products of the hydroxyl group-containing Atari rate Relates: bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or epoxy cyanate acrylates which are (meth) acrylic acid adducts of phenol novolak epoxy resins, and methacrylates corresponding to the above acrylates However, these can be used alone or in combination of two or more. Among these, multifunctional (meth) atalylate compounds having two or more (meth) atalyloyl groups in one molecule are preferred. 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 is used not only to increase the photoreactivity of the composition, but also to adjust the viscosity of the composition to be suitable for various coating methods, and to help the solubility in aqueous alkaline solutions. Also fulfills. The mixing amount of the radical polymerizable monomer (G) is preferably 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing compound (A).

[0126] The curable composition of the present invention may contain an inorganic thickener to such an extent that the properties of the cured product are not deteriorated. Examples of the inorganic thickener include hydrophilic silica such as # 50, # 200, and # 380 manufactured by Nippon Aerosil, hydrophobic silica such as # R974 and # R972 manufactured by Nippon Aerosil, and Wilbur's Ellis. Organic bentonite such as Olben and Benton 38. The compounding amount of these inorganic thickeners is sufficient at a quantitative ratio, and for example, 0.1 to 20 parts by mass, preferably 0.5 to 100 parts by mass of the carboxyl group-containing compound (A). 1010.0 parts by mass.

[0127] The curable composition of the present invention may further contain, if necessary, barium sulfate, barium titanate, silicon oxide powder, silicon oxide fine powder, amorphous silica, crystalline silica, and fused silica. Known and commonly used inorganic fillers such as silica, talc, clay, magnesium carbonate, calcium carbonate, oxidized aluminum, aluminum hydroxide, and My power, fine rubber particles, and powdered epoxy resin (for example, Nissan Chemical Industries Resin, urethane resin, melamine resin, benzoguanamine resin (for example, M-30, S, MS, etc., manufactured by Nippon Shokubai Co., Ltd.), urea resin, cross-linked acrylic polymer (for example, MR-2G manufactured by Soken Iridakusha) And organic fillers such as MR-7G and Techpolymer manufactured by Sekisui Plastics Co., Ltd. can be used alone or in combination of two or more. They are used for the purpose of suppressing curing shrinkage of a coating film and improving properties such as adhesion, hardness and heat resistance. An appropriate 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). [0128] The curable composition of the present invention may further comprise a phthalocyanine, if necessary, such as phthalocyanine, green, aozin. Green, disazoyello, crystal violet, titanium oxide, carbon black, and naphthalene black. Known and commonly used thermal polymerization inhibitors such as coloring agents, hydrocyanic acid quinone, hydroquinone monomethinole ether, t-butyl catecholone, pyrogallonole, phenothiazine, defoaming agents such as silicone, fluorine and polymer, and Z or R Known and commonly used additives such as a belling agent, an imidazole-based, a thiazole-based, and a triazole-based silane coupling agent can be blended.

[0129] Furthermore, 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, if necessary, for the purpose of obtaining flame retardancy. can do . The compounding amount of the flame retardant is usually from! To 200 parts by mass, preferably from 5 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing compound (A). When the compounding amount of the flame retardant is within the above range, the flame resistance, heat resistance, water resistance and adhesion of the obtained cured product are highly balanced, which is preferable.

'In order to reduce the flammability of the composition of the present invention and to increase the viscosity, water may be added to the composition.

[0130] The curable composition of the present invention can be easily cured by photocuring and Z or heat curing in the same manner as conventionally known methods. For example, the above-mentioned curable composition is sufficiently mixed using a roll until uniform, and is applied to a desired base material according to the application, for example, screen printing, curtain coating, spray coating, roll coating, etc. The coating is performed by a known coating method, for example, by volatilizing and drying the diluting solvent contained in the composition at a temperature of about 60 to 100 ° C., thereby producing a coating excellent in dryness to the touch without dripping. A film can be formed. Further, the curable composition of the present invention can also form a dry film for resist, and in that case, it may be laminated as it is. Then, it is light-cured by exposure to active energy rays. Next, by heating and curing at about 100 ° C to 200 ° C, in addition to excellent crack resistance, electrical insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance, etc. A cured product excellent in the above-mentioned characteristics can be obtained. In the case of forming a solder resist on a printed wiring board, it is selectively exposed to active energy such as ultraviolet rays through a patterned photomask, or directly by a laser beam. By drawing and developing the exposed portion with a dilute alkaline aqueous solution to form a resist pattern and curing by heating, a resist film having excellent characteristics as described above can be obtained. Examples of the diluted 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.

Example ;

Hereinafter, the present invention will be described specifically 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.

[0132] Synthesis example 1

'' 3-Acryloyl oxy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester 701A) in a 100 ml flask equipped with a nitrogen inlet tube and a thermometer 10.0 g ( 46. 68 millimonoles), tetrahydrofuran 80 ml, terephthalanolic acid chloride 4.7 g (23.34 millimonoles), triethynoleamine 5.9 g (58.35 millimonoles), 4-dimethinoleaminopyridine 0.5 g (4.09 Mmol) and 0.4 mg of methinolehydroquinone, and the mixture was refluxed for 20 hours at 65 ° C under a nitrogen stream. 50 ml of water was added to the reaction solution to dissolve the basic salt of triethylamine in water 1, and the reaction mixture was extracted with ethyl acetate. Further, the reaction mixture in the aqueous layer was extracted with 25 ml of ethyl acetate. The obtained organic layer was washed with IN aqueous hydrochloric acid solution (50 ml), followed by saturated saline (50 ml). The organic layer was dried over 5. Og of sodium sulfate, filtered under reduced pressure, and concentrated to obtain 11.7 g of a compound. This was subjected to column purification using 230 g of neutral silica gel. As a result, 4.5 g of a tetra (meth) atalylate toyidani compound was obtained. This was a yield of 34.5% of theory. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDC1, reference substance TMS (tetramethylsilane)) of the obtained tetra (meth) atalylate compound and

Three

The chromatograms (measured using high performance liquid chromatography) are shown in Figure L and Figures 2 and 3, respectively. Table 1 shows the results of NMR identification. It should be noted that only one peak appeared in the chromatogram shown in FIG. 3! /, Which indicates that a pure compound was obtained. [Table 1]

[0134] Synthesis Example 2

In a 10-liter flask equipped with a nitrogen inlet tube and a thermometer, 1.0 kg (4.67 mol) of 3-Attalylox-xy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester 701A) Add 7.0 l of tetrahydrofuran, 475. Og (2.34 mol) of terephthalanolic acid chloride, 590 g (5.83 mol) of triethylamine, 0.4 g of methylhydroquinone and 0.4 g of phenothiazine, and add 6 g of nitrogen at room temperature under a nitrogen stream. Reacted. 5.0 liters of water was added to the reaction solution to dissolve the basic salt of triethylamine in water, and the reaction mixture was extracted with 5.0 liters of ethyl acetate. Further, 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 aqueous hydrochloric acid solution, subsequently with 5.0 L of a saturated aqueous sodium hydrogen carbonate solution, and further washed 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 (a viscous yellow liquid). The resulting concentrated reaction mixture was homogenized by adding 2.5 liters of methanol, cooled to -30 ° C to form crystals, filtered (washed with methanol), and filtered to give a white powder having a melting point of about 82 ° C. To obtain 350 g of a tetra (meta) atalay toy dagger. This was a yield of 27.0% of theory. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) of the obtained tetra (meth) acrylate compound

Three

The chromatograms (measured using high performance liquid chromatography) are shown in FIGS. 4, 5, and 6, respectively.

[0135] Test example 1

Replacement form (Rule 26) The white crystalline tetra (meth) acrylate compound was melted at ioo ° C and applied to a polyimide film using a bar coater to a thickness of 50 μ μη, (1) 120. C for 120 minutes, (2) 140 ° C for 30 minutes, (3) 160 ° C for 20 minutes, or (4) 180 ° C for 10 minutes, and then use a PCT device (TABAI ESPEC HAST SYSTEM TPC). —412MD) using 121. C, and treated at 100% RH for 24 hours. Thereafter, the polyimide film cured film was peeled off to obtain four types of evaluation samples. The heat resistance, flexibility, and bending resistance of these evaluation samples were measured by the methods described below, and the degree of thermal degradation under high humidity was evaluated. Also, a hardened film was prepared in the same manner as described above except that the treatment with a PCT apparatus was not performed on a 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.

[Table 2]

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

[0137] (1) Heat resistance

The evaluation sample was measured by thermogravimetry (TG) to evaluate heat resistance.

In this specification, as shown in FIG. 7, the outer perimeter determined from the tangent at the inflection portion of the TG curve is defined as the heat-resistant temperature.

[0138] (2) Flexibility

One side of the film-shaped test piece prepared by processing the evaluation sample to a width of 10 mm and a length of 90 mm was placed on an electronic device, and the other side was bent until the distance between the films became 10 mm. The maximum load acting on the balance was evaluated as the repulsive force and evaluated according to the following criteria.

〇: less than 10g

△: less than 10-30g

Paper (Rule 26 X: 30g or more, or the material is broken and cannot be measured

[0139] (3) Folding resistance

A film-like test piece prepared by kneading the evaluation sample to a width of 10 mm and a length of 90 mm was bent at 135 ° and evaluated according to the following criteria.

〇: The cured film does not break.

△: The cured film is broken, but has cracks

'X: Cured film breaks''

[0140] (4) Water absorption

Measure the mass of the evaluation sample, and then treat the evaluation sample for 24 hours at 121 ° C and 100% RH using a PCT device (TABAI ESP EC HAST SYSTEM TPC—412MD), and cure 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) / (w -w)} x ioo

2 1 1

Where W is the mass of the evaluation sample, W is the mass of the evaluation sample after PCT treatment, W

12 g is the mass of the glass plate.

[0141] Preparative 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 ninyl, and heated and refluxed at about 80 ° C for 1 hour under a stream of argon. . Thereafter, 1 ml of dimethylformamide was added, and the mixture was further heated under reflux at about 80 ° C. for 24 hours. After completion of the reaction, unreacted thionyl chloride was distilled off under reduced pressure to obtain 31. Og of 2,6-naphthalenedicarboxylic acid chloride as yellow crystals.

[0142] Preparative synthesis example 2

80 g (0.37 mol) of 2,6-naphthalenedicarboxylic acid, 240 milliliters of trichlorinated chloride and 3.3 milliliters of pyridine, and 2 milliliters of pyridine were placed in 1 liter of frasgo. Heated to reflux for hours. Thereafter, 1 ml of dimethylformamide was added, and the mixture was heated and refluxed at about 80 ° C. for further 4 hours. Subsequently, 100 ml of Shii-Dai-Thionil was calorie-heated and refluxed 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 2,6-naphthalenedicarboxylic acid chloride as yellow crystals. [0143] Preliminary synthesis 3

53.8 g of 2, '6-naphthalenedicarboxylic acid chloride obtained in Preparative Synthesis Example 2 was dissolved in toluene, cooled at 130 ° C for 12 hours, and the precipitated crystals were filtered to obtain high purity 2,6. —22.7 g of naphthalenedicarboxylic acid chloride was obtained.

[0144] Synthesis example 3

In a 1-liter flask, 3-acrylic acid xyl-2-hydroxypropyl methacrylate (Shin Nakamura Chemical: KK Co., Ltd., trade name: NK ester 701A) 43.3 _g (202 mmol), tetrahydrofuran, 400 milliliter furan, Phenothiazine (4.3 mg) and triethylamine (51.lg, 505 mmol) were charged and stirred at about 0 ° C. under an argon stream. Next, 19 g (80 mmol) of 2,6-mononaphthalenedicarboxylic acid chloride obtained in Preparative Synthesis Example 1 was dissolved in 200 ml of tetrahydrofuran, and added dropwise to the reaction system at 1 Q ° C or lower. After completion of the dropwise addition, 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, a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with ethyl ether. The separated organic layer was washed with water and a saturated aqueous sodium chloride solution in the next step, dried over magnesium sulfate, filtered and concentrated to obtain 7 g of a brown-brown oil. FIG. 8 shows the chromatogram (measured using high performance liquid chromatography) of the obtained oil. The resulting oil was column purified (SiO: 200 g, development獰媒: ⁴ 0% hexane in acetic Echiru / n-to) to give a yellow oil ² ⁵ g.. 10 ml of methanol was added to the obtained oil, cooled at 130 ° C. for 5 hours, and filtered to obtain 1.5 g of & color crystal. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) of the obtained tetra (meth) atalylate compound, nuclear magnetic * sounding spectrum (solvent CDC1,

'■ 3 Reference substance TMS (tetramethylsilane)) and chromatogram (measured using high performance liquid chromatography) are shown in Fig. 9, Fig. 10 and Fig. 11, respectively.

[0145] Synthesis example 4

A 1-liter flask was charged with 28.3 g (79 millimonoles) of 3-attaryloyi-hydroxy-2-methypropyl methacrylate, 230 milliliters of tetrahydrofuran, 2.0 mg of phenothiazine, 2.0 mg of tritinolamine, 24.O (237 mmoles), and argon. The mixture was stirred at about 0 ° C under an air stream. Next, 20.0 g (79 mmol) of 2,6-naphthalenedicarboxylic acid chloride obtained in Preparative Synthesis Example 2 was dissolved in 200 ml of tetrahydrofuran and added dropwise to the reaction system at 10 ° C. or lower. drop After completion of the reaction, the temperature in the reaction system was adjusted to about 25 ° C, and the reaction was performed for 2 hours. After the completion of the reaction, an aqueous solution of saturated sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. The separated organic layer was washed with water and then with a saturated aqueous solution of sodium salt, dried over magnesium sulfate, filtered and concentrated to give 37 g of a brown oil. FIG. 12 shows the chromatogram (measured using high performance liquid chromatography) of the obtained oil. The obtained oil was purified by column (SiO: 320 g, developing solvent: 20% ethyl acetate in Zn-hexane), and colorless and transparent

2

A liquid of 14 Og was obtained. 20 ml of ethyl ether was added to the obtained oil, and 4 mg of the white crystal obtained in Synthesis Example 3 was seeded as a seed crystal, and recrystallized at −30 ° C. for 12 hours. As a result, a white semi-solid substance was obtained. Therefore, the ethyl ether was removed, and then n-hexane was added. After stirring, the mixed solvent of ethyl ether and n-hexane that could not be removed was removed, and 20 ml of ethyl ether was added again, followed by filtration. As a result, 2.7 g of a white crystal having a melting point of about 92 ° C was obtained. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) of the obtained tetra (meth) atalylate compound ) And chromatogram (

Three

FIG. 13, FIG. 14 and FIG. 15 show the measurement results using high performance liquid chromatography, respectively. Table 3 shows the results of ¾-NMR identification.

[Table 3] Reaction products

Replacement Form (Rule 26) ' [0146] The filtrate was concentrated to obtain 11.3 g of a colorless and transparent liquid. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) and chromatogram (high

Three

(Measured using high performance liquid chromatography) are shown in Fig. 16, Fig. 17 and Fig. 18, respectively.

[0147] Synthesis example 5

In a 1 liter flask, 38.4 g (179 mmol) of 3-acryloyloxy-2-hydroxypropyl methacrylate, 230 ml of tetrahydrofuran, 2.5 mg of phenothiazine, 2.5 mg of triethylamine, and 27.2 g (269 mmol) of triethylamine were added, and the mixture was placed under an argon stream. And stirred at about 0 ° C. Next, 22.7 g (90 mmol) of 2,6-naphthalenedicarboic acid chloride obtained in Preparative Synthesis Example 3 was dissolved in 360 ml of tetrahydrofuran and added dropwise to the reaction system at 10 ° C. or lower. After completion of the dropwise addition, the temperature in the reaction system was adjusted to about 25 ° C, and the reaction was performed for 2 hours. After the completion of the reaction, an aqueous solution of saturated sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. The separated organic layer was washed with water and then with a saturated sodium chloride aqueous solution, dried over magnesium sulfate, then filtered and concentrated to obtain 60.lg of a brown oil. Fig. 19 shows the chromatogram (measured using high performance liquid chromatography) of the obtained oil. Next, the obtained oil was subjected to column purification (SiO: 500 g, developing solvent: 20% ethyl acetate in Zn-hexane), and

2

25.2 g of a color-transparent oil was obtained. 70 ml of ethyl ether was added to the obtained oil, stirred, and then filtered to obtain 6.6 g of white crystals. Infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR), nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) of the obtained tetra (meth) aphthalate compound ) And black

3,.

The matograms (measured using high performance liquid chromatography) are shown in FIGS. 20, 21 and 22, respectively. .

[0148] 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 coated on a polyimide film using a bar coater to a thickness of 50 / m. Then, the mixture was heated at 180 ° C for 30 minutes, and then at 200 ° C for 10 minutes. The obtained cured film was heated at 121 ° C and 100 ° / C using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD). Treated at RH for 24 hours, and then cured polyimide film Peeling off gave 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 resistance were measured and evaluated by the methods described later. In addition, a cured film was formed on a glass plate whose mass had been measured in advance in the same manner as described above except that the treatment with the PCT apparatus was not performed, 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 described above. The measurement results are shown in Table 4 below.

[0149] [Table 4]

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

[0150] (2 ') Flexibility

A film-shaped test piece prepared by kneading the evaluation sample to a width of 5 mm and a length of 40 mm is placed on the electronic device and the other side is bent until the distance between the films becomes 10 mm. The maximum load applied to the electronic balance was evaluated as a repulsive force and evaluated according to the following criteria.

〇: less than 10g

△: less than 10-30g

X: 30g or more, or the test piece is broken and cannot be measured

[0151] (3) Folding resistance

A film-like test piece prepared by processing an evaluation sample to a width of 5 mm and a length of 40 mm was bent at 135 ° and evaluated according to the following criteria.

〇: The cured film is broken

Δ: The cured film does not break, but has cracks

X: The cured film breaks

[0152] Synthesis example 6.

In a 50 ml flask, 3-acryloylic xy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Ichigaku Kogyo Co., Ltd., trade name: NK ester 701 A) 2.0 g (9.33 mmol), N, N

' — 20 ml of dimethylformamide, lmg of 4-tert-butylcatechol, 1.71 g (ll. 2 mmol) of 1-hydroxy-11H-benzotriazole hydrate, 2.4 g (23.34 mmol) of triethylamine 1 Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 2.2 g (ll. 2 milliginole), 826 mg (7 millimonole) of conodic acid calorie The reaction was carried out at room temperature for 14 hours. Ethyl acetate and water were added to the obtained reaction solution to carry out extraction, and the separated organic layer was washed with saturated saline, then dried over magnesium sulfate, filtered and concentrated. A yellow liquid was obtained. This was purified with a column using 50 g of silica gel, and a tetra (meth) atalylate compound having an acid value of lmgKOHZg or less and 3-attaryloyi xy-12-hydroxyprohi were used. 1.5 g of a liquid mixture with lumetatalylate were obtained.

[0153] The nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethyl, meth)) of the mixture of the obtained tetra (meth) atalylate compound and 3-acryloyl xy-l-hydroxypropyl metharylate, The chromatogram (measured using high performance liquid chromatography) and the infrared absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) are shown in FIGS. 23, 24 and 25, respectively. In addition! Table 5 shows the results of the NMR identification.

[0154] [Table 5]

[0155] For reference, only 3-acryloyloxy-1-hydroxypropyl methacrylate was used.

Replacement paper. (Parent ₂₆ ^: German nuclear magnetic resonance spectrum (solvent CDC1 _3, the reference substance TMS (tetramethylsilane)) and chromatogram (measured by high performance liquid chromatography) in FIGS. 26 and 27, further represented by the following formula (3) Figure 28 shows the nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) of the monocarboxylic acid having the structure shown.

Three

[0156] [Formula 4]

HO-C-I X

(3)

\

CH ₂ -OC -C = CH ₂

0 R ²

(Where R \ R ² represents a hydrogen atom or a methyl group.)

[0157] Comparing FIG. 23 with FIG. 26, the mixture of the above tetra (meth) atalylate compound and 3-acryloyloxy-2-hydroxypropinole methacrylate shows that the mixture of 3-acryloyloxy-2-hydroxypropyl There is no single peak of meta! In succinic acid at around 2.6 ppm. Also, comparing FIG. 23 with FIG. 28, the above-mentioned monocarboxylic acid cannot be used as a mixture of the above tetra (meth) acrylate conjugate and 3-acryloyl oxy-1-hydroxypropyl methacrylate. A single peak appears around 10.3 ppm. Further, comparing FIG. 24 with FIG. 27, the mixture of the above-mentioned tetra (meth) acrylate conjugate and 3-attali-oxyl-2-hydroxypropyl metharylate shows that 3-atolyloy-xy-xy-2-hydroxypropyl methacrylate A peak not found appears at around 6 minutes. From the above data, the peak appearing at around 6 minutes in FIG. 24 is due to the above-mentioned tetra (meth) atalylate compound.

[0158] Synthesis example 7

In a 50 ml flask, 1.71 g (8 mmol) of 3-Attalylox xy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), 20 ml of tetrahydrofuran, 4-ml methoxyphenol 0.8 mg and 2.02 g (20 mmole) of triethynoleamine are charged. While stirring at 0 ° C. under an argon stream, 1.02 g (5.6 mmol) of adipic acid chloride is added.

Replacement form (Rule 26.) Was added dropwise, and after completion of the addition, the mixture was reacted at room temperature for about 14 hours. After the completion of the reaction, the reaction solution was filtered, and a saturated aqueous solution of sodium hydrogen carbonate and getyl ether were added to perform extraction. Next, the separated organic layer was dried over sodium sulfate, filtered, concentrated, and then subjected to column purification (silica gel 40 g, developing solvent: 20% ethyl acetate Zn-hexane) to give a colorless, transparent oil. A liquid mixture of the tetra (meth) acrylate compound of Example 1 and 3-acryloyl oxy-2-hydroxypropyl methacrylate was obtained. FIG. 29 shows the nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane)) of the obtained mixture. Also, ^α Η-

Three

Table 6 shows the results of NMR identification.

[0159] [Table 6]

[0160] Synthesis Example 8

In a 50 ml flask, 3-attaryloy xy-2-hydroxypropyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester 701 A) l. 71 g (8 mmol), tetrahydrofuran 20 ml, 4-methoxyphenol 0.8 g of Nore and 2.02 g (20 mm monotriamine) of triethynoleamine were charged, and 1.02 g (5.6 mmol) of adipic chloride was added dropwise while stirring at 0 ° C under an argon stream, and the addition was completed. Thereafter, the reaction was carried out at room temperature for about 13 hours. After completion of the reaction, the reaction solution was filtered, treated with a short column (silica gel 25 g, developing solvent: tetrahydrofuran), and concentrated.

Refill paper (Rule 26) As a result, 2.5 g of a liquid mixture containing about 64% of a mixture of tetra (meth) acrylate conjugate and 3-acryloyl xy-2-hydroxypropyl methacrylate was obtained. A nuclear magnetic resonance spectrum (solvent CDC1, reference material TMS (tetramethylsilane) of the mixture of the obtained tetra (meth) acrylate compound and 3-acryloyloxy-2-hydroxypropyl methacrylate was used.

'. 3

)) And the chromatogram and the infrared absorption spectrum by gel permeation chromatography are shown in FIGS. 30, 31 and 32, respectively. For reference, FIG. 33 shows a chromatogram by gel permeation chromatography of 3-attaryloy xy-2-hydroxypropyl methacrylate alone.

[0161] Test example 3

The liquid mixture of the tetra (meth) atalylate compound of Synthesis Example 6 and Synthesis Example 8 and 3-attaryloyloxy-12-hydroxypropyl metharylate was adjusted to a thickness of 50 πι using a bar coater. The film was applied to a polyethylene terephthalate film and heated at 180 ° C for 30 minutes to remove the cured film from the polyethylene terephthalate film, and then the PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD) was used. The sample was treated under the conditions of ° C and 100% RH for 24 hours 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 bending resistance was measured by the method (3) used in Test Example 2 and the flexibility was described later. The degree of thermal degradation under high humidity was evaluated. In addition, a cured film was prepared on a glass plate whose mass had been measured in advance in the same manner as described above, except that the treatment with a PCT apparatus was not performed, 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 the above measurements are shown in Table 7 below. .

[0162] [Table 7] Characteristics Synthesis example 6 Synthesis example 8

0) Heat resistant temperature (° c) 310.8 347.9

(2 ") flexibility O O

(3 ') Folding resistance O O

(4) Water absorption (%) 0.8 0.8

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

[0163] (2 ") flexibility

Place one side of the film-shaped test piece prepared by processing the evaluation sample to 5 mm width and 40 mm length on an electronic balance, and bend the other side. The maximum load applied to the balance was evaluated as the repulsive force and evaluated according to the following criteria.

〇: less than 20g

△: less than 20-40g

X: 20g or more, or the test piece is broken and cannot be measured

[0164] Examples 1 to 5 and Comparative Examples 1 and 2

Each component was blended according to the blending composition shown in Table 8 (the numerical values are parts by mass). Examples 1 to 3 were each stirred at 90 ° C, Example 4 was stirred at room temperature, and Example 5 was stirred at 100 ° C to prepare a curable composition. For Comparative Examples 1 and 2, each was separately kneaded with a three-roll mill to prepare a curable composition. These were applied to a polyimide film using a bar coater to a thickness of 50 μπι. In Examples 1 to 3 and Comparative Examples 1 and 2, exposure was performed under the conditions of an exposure amount of 300 mjZcm ^2. For Example 4, after leaving at room temperature for 6 hours, gradually raise the temperature to 115 ° C over 60 minutes, and apply force at 115 ° C for 60 minutes! ] Heated and heated at 180 ° C for 30 minutes for Example 5 followed by 200 ° C for 10 minutes. Next, treatment was performed using a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC—412MD) at 121 ° C. and 100% RH for 24 hours. Thereafter, each polyimide film cured film was peeled off to obtain an evaluation sample.

Replacement form (Rule 26) [0165] [Table 8]

[0166] Examples 6 and 7

For Example 6, the composition obtained in Example 1 was melted at 100 ° C., impregnated into a glass cloth, and then exposed under the condition of an exposure amount of SOOnj / cm ^2. After melting the tetra (meth) atalylate compound obtained in Synthesis Example 2 at 100 ° C and impregnating the glass cloth, the mixture was heated at 140 ° C for 30 minutes, and then a PCT device (TABAI E SPEC HAST SYSTEM TPC-412MD) was used for 24 hours at 121 ° C and 100% RH to obtain an evaluation sample.

[0167] The heat resistance of the evaluation samples obtained in each of the Examples and Comparative Examples was measured by the method (1) described in Test Example 1, and the heat resistance of Examples 1 to 4, 6, 7, and The flexibility and folding endurance of the evaluation samples obtained in Comparative Examples 1 and 2 were measured by the methods (2) and (3) used in Test Example 1, and the flexibility of the evaluation sample obtained in Example 5 was measured. Properties and bending resistance were determined by the method used in Test Example 2 above (

Replacement chapel (Chief rule 26) Measurements were made in 2 ') and (3') to evaluate the degree of thermal degradation and the like under high humidity. Also, a cured film was prepared in the same manner as in each of the above Examples and Comparative Examples, except that a treatment using a PCT apparatus was not performed on a glass plate whose mass had been measured in advance, and an evaluation sample was obtained. The water absorption of the cured film was measured and evaluated by the method (4) used in Test Example 1 above. Table 9 shows the results of the above tests.

[0168] [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 (the numerical values are parts by mass). In Examples 8, 11, and 12, and Comparative Examples 3 and 4, the respective components were stirred to prepare curable compositions. In Example 9, the mixture was stirred at 90 ° C. to prepare a dangling composition. These so as to have a thickness of 50 / im with barcode one coater, was coated on a polyethylene terephthalate Fi Lum, for Example 8 and Comparative Example 3, 4, and exposed under the conditions of exposure amount 300 mJ / cm ² In Examples 9 and 12, heating was performed at 150 ° C for 60 minutes, and in Example 11, after standing at room temperature for 6 hours, the temperature was raised to 80 ° C over 60 minutes, and the temperature was increased to 80 ° C for 30 minutes. Then, the calories were heated at 100 ° C for 30 minutes in the next stage, and at 150 ° C for 30 minutes in the next stage. Next, treatment was performed for 24 hours at 121 ° C and 100% RH using a PCT device (TAB AI ESPEC HAST SYSTEM TPC-412MD), and then the polyethylene terephthalate film was peeled off to obtain an evaluation sample. Was.

Example 10

In Example 10, a glass cloth was impregnated with a composition similar to the composition of Example 8 and then exposed under the conditions of an exposure amount of 300 mL cm ² , and then a PCT apparatus (TABAI ESPEC

Using HAST SYSTEM TPC-412MD), the sample was treated at 121 ° C and 100% RH for 24 hours to obtain an evaluation sample.

Replacement Form '' (Rule 26 [0171] [Table 10]

[0172] The heat resistance of the evaluation samples obtained in each of the above Examples and Comparative Examples was determined by the method (1) described in Test Example 1, and the flexibility and the fold resistance were determined by the methods described in Test Example 2. The measurement was performed by the methods (2 ′) and (3 ′), respectively, to evaluate the degree of thermal degradation under high humidity! /.

Also, on a glass plate whose mass was measured in advance, a hardened film was prepared in the same manner as in the above Examples and Comparative Examples except that the treatment with a PCT apparatus was not performed, 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. Table 11 shows the results of the above tests.

[0173] [Table 11]

Paper (Rule 2 Example No. Comparative example No. Characteristics 8 9 1 0 1 1 1 2 3 4

(1) Heat resistant temperature (° c) 3 1 9 343 3 1 1 3 5 1 349 3 48 2 6 1

(2 ') Flexibility 0 〇 O O O X 〇

(3 ') Folding resistance O O O O o X O

(4) Water absorption) 0.8 0.7 0.8 0.7 1.0 1.1.9 3.3.7

[0174] Synthesis example 9

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device and a stirrer, a nopolak-type cresol resin (trade name: Shonor CRG951J, manufactured by Showa Kagaku Co., Ltd., OH equivalent: 119.4) 119.4 g, potassium hydroxide (1.19 g) and toluene (119.4 g) were charged, the system was purged with nitrogen while stirring, and the temperature was raised by heating, and 63.8 g of propylene oxide was gradually added dropwise, and (The reaction was carried out at 0 to 4.8 kg / cm ² for 16 hours. After cooling to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution and mixed to neutralize potassium hydroxide. A propylene oxide reaction solution of a novolak-type tarezole resin having a nonvolatile content of 62.1% and a hydroxyl equivalent of 182.2 g / eq. Was obtained, and terkylenoxide was equivalent to one equivalent of the phenolic hydroxyl group. An average of 1,08 mol was added.

[0175] An alkylene oxide reaction solution of the obtained nopolak-type taresol resin (293.0 g), acrylinoleic acid (43.2 g), methanesnolephonic acid (11.53 g), methinolenodidroquinone (0.18 g), and tonoleene (252.9 g) were stirred, A reactor equipped with a thermometer and an air blowing tube was charged, air was blown at a rate of lOmlZ, and the mixture was reacted at 110 ° C for 12 hours with stirring. 12.6 g of water was distilled off as an azeotrope of water produced by the reaction. After that, the reaction solution was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, the toluene was distilled off using an evaporator while replacing the toluene with 118.lg of diethylene glycol monoethyl ether acetate to obtain a novolak-type atarilate lug solution.

[0176] Next, 332.5 g of the obtained novolak-type atarilate lunar 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

Replacement 甩 Was blown in at a rate of lOmlZ, and while stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the mixture was reacted at 95 to 101 ° C for 6 hours. After cooling, it was taken out. The thus obtained carboxyl group-containing photosensitive resin had a nonvolatile content of 70.6% and an acid value of the solid content of 87.7 mg KOHZg. '

[0177] Synthesis example 10 '

A reaction vessel equipped with a gas inlet pipe, a stirrer, a cooling pipe, a thermometer, and a dropping funnel for continuous dropping of an aqueous alkali metal hydroxide solution was charged with a 1.5-hydroxyl with a hydroxyl equivalent force of S80 g / eq. 224 g of roxinaphthalene and 1075 g of bisphenol phenol A type epoxy resin (Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 189 g / eq.) Were charged and dissolved at 110 ° C. under a nitrogen atmosphere with stirring. Thereafter, 0.65 g of triphenylphosphine was added to the mixture. • 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 to obtain an epoxy equivalent of 452 gZeq. An epoxy compound (3_a) was obtained. Next, the temperature in the flask was cooled to 40 ° C, and 1920 g of epichronorehydrin, 1690 g of tonolene, 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 the mixture was further reacted for 6 hours. After completion of the reaction, most of the excess epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salts and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methylisobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure to obtain a polyepoxy resin (3_b) having an epoxy equivalent of ²⁷⁷ g / eq. When the obtained polynuclear epoxy resin (3_b) was calculated from the epoxy equivalent, about 1.59 out of 1.98 alcoholic hydroxyl groups in the epoxy compound (3-a) were epoxidized. RU Therefore, the epoxidation ratio of alcoholic hydroxyl groups is about 80%.

[0178] Next, 277 g of the obtained polynuclear epoxy resin (3-b) was put into a flask equipped with a stirrer, a cooling pipe and a thermometer, and 290 _g of carbitol acetate was added thereto.ヽ 0.46g of idroquinone and 1.38g of trifeninolephosphine are calo-free, 95 ~: L05. C was heated by calo, 72 g of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 129 g of tetrahydrophthalic anhydride was added and reacted for 8 hours. The reaction was oxidized by potentiometric titration and total oxidation was measured. The end point is a response rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 62% and an acid value of the solid content of lOOmgKOHZg.

[0179] Examples 13 to 15 and Comparative Examples 5 and 6

Each component was blended according to the blending composition shown in Table 12 and kneaded separately with a three-roll mill to prepare a curable composition. Using a 100-mesh polyester screen with a screen printing method, apply the entire surface to a copper through-hole printed wiring board that has been patterned to a thickness of 20 to 30 μm. Was dried using a hot air dryer at 80 ° C for 30 minutes, and then a negative film having a resist pattern was brought into close contact with the coating film, and an ultraviolet exposure apparatus (Model HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.) was used. Irradiate with UV light (exposure 700 mjZcm ² ), develop with 1% aqueous solution of sodium carbonate for 60 seconds, 2. Spray pressure of Okg / cm ² , then use hot air dryer at 150 ° C for 60 minutes Heat curing was performed to produce a test substrate. '·

[0180] The test substrate having the obtained cured film was subjected to crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless metallization according to the test methods and evaluation methods described below. A resistance test was conducted.

[0181] Also, instead of the copper through-hole printed wiring board, use a B pattern of a printed circuit board ((thickness 1.6 mm) specified by IPC. A resistance test was performed. Table 13 shows the results of the above tests.

[0182] [Table 12]-'

P T / JP2004 / 016419

Paper (Yu rule 26) Example No. Comparative Example No.

Characteristic

1 3 1 4 1 5 5 6

Cracking O o o X X

PCT resistance O o o o o

Solder heat resistance 0 o o o o

Acid resistance o o o 0 o

Alkali resistance o o o o o

Electroless gold plating resistance 0 o o o o

Electrical insulation resistance o o o o o

As is clear from the results shown in Table 13, in Comparative Examples 5 and 6 in which a carboxyl group-containing photosensitive resin was used as the photosensitive component, the crack resistance during a heat cycle was inferior. In Examples 13 to 15 further containing a tetra (meth) atalylate compound, the crack resistance was excellent. The evaluation method of the performance test in Table 13 above is as follows

[0184] (5) Crack resistance:

The crack resistance of the cured film was evaluated using Thermal Shock Chamber NT1020W manufactured by Kusumoto Kasei Co., Ltd., with one cycle of 65 ° C to 150 ° C and the following criteria.

〇: Cracks occurred in 500 cycles or more

△: Cracks occurred in 300 to 499 cycles

X: Cracks occurred in 299 cycles or less

[0185] (6) PCT resistance:

The PCT resistance of the cured film was evaluated under the following criteria under the conditions of 121 ° C and 50 hours in saturated steam.

〇: The cured film has no blistering, peeling or discoloration. Δ: The cured film has slight blistering, peeling or discoloration.

X: The cured film has blisters, peeling, and discoloration

Difference 'Kin'-¾ 周弒 (Parent) [0186] (7) Adhesion:

According to the test method of JIS D 0202, a cross cut was made in a cross-cut pattern on the cured film, and then the peeling performance after a peeling test with a cellophane adhesive tape was visually determined.

◎: 100/100 with no peeling

〇: 100Z100 with cross-cut part slightly peeled off

Δ: 50/100 ~ 90/100

X: 0 / 100〜50 / 100 '.

(8) Solder heat resistance:

According to the test method of JIS C 6481, the test board was immersed in a solder bath at 260 ° C for 10 seconds three times, and the change in appearance was evaluated. Note that a flux according to JIS C 6481 was used as the post flux (rosin-based). , '

〇: No change in appearance

, △: Discoloration of the cured film is observed

X: Floating, peeling, solder dipping of cured film

(9) Acid resistance:.

The test substrate was immersed in a 10% by volume aqueous sulfuric acid solution at 20 ° C for 30 minutes, taken out, and the state of the cured film was evaluated according to the following criteria.

'〇: No change is observed

△: Slightly changed '' X: Cured film with blisters or swelling-off

(10) Alkali resistance:

The test substrate was evaluated in the same manner as in the acid resistance test, except that the 10% by volume aqueous sulfuric acid solution was replaced with a 10% by weight aqueous solution of sodium hydroxide.

[0190] (11) Electroless gold plating resistance: Electroless gold plating was performed on a test substrate according to the process described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and cured. The peeling state of the film was determined according to the following criteria. '

〇: No change in appearance, no peeling of cured film. . Δ: No change in appearance, but slight peeling of cured film.

X: Lifting of the cured film was observed, plating dive was observed, and peeling of the cured film was large in the peeling test.

Electroless plating process: ''

1. Degreasing: ' ¹

The test substrate was immersed in a 30 ° C. acidic degreasing solution (a 20% by volume aqueous solution of Metex L-15B manufactured by McDermid Japan Co., Ltd.) for 3 minutes.

2.Water ^: '.

The test substrate was immersed in running water for 3 minutes.

3. Soft etch:

The test substrate was immersed in a 14.3% by mass aqueous solution of ammonium persulfate at room temperature for 3 minutes.

4.Washing:

The test substrate was immersed in running water for 3 minutes. ,

5. Acid immersion: ':' The test substrate was immersed in a .10% by volume aqueous sulfuric acid solution for 1 minute at room temperature.

6.Washing:

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 solution (a 10% by volume aqueous solution of Melplate Activator 350, manufactured by Meltex Co., Ltd.) at 30 ° C. for 7 minutes.

8.Washing:

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 (Melplates Co., Ltd., Melplate Ni-865Μ, 20% by volume aqueous solution) at 85 ° C and ρΗ = 4.6 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: 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 95 ° (a plating solution of pH = 6 (aqueous solution of UP 15 volume%, olelect mouthless UP, manufactured by Meltex Co., Ltd., aqueous solution of 3% by mass of potassium cyanide)).

13. Rinse: '

The test substrate was immersed in running water for 3 minutes. .

14. Hot water washing:

The test substrate was immersed in warm water of 60 ° C, washed thoroughly with water for 3 minutes, drained well, and dried. Through these steps, a test substrate having electroless gold plating was obtained.

[12] (12) Electrical insulation:

The electrical insulation of the cured film was evaluated according to the following criteria.

Humidification conditions: temperature 110 ° C, humidity 85% RH, applied voltage 5V, 50 hours.

. Measurement conditions: Measurement time 60 seconds, applied voltage 500V.

: Q: Insulation resistance after humidification 10 Ω or more, no copper migration

△: Insulation resistance after humidification 10 ^1Q Q or more, copper migration

X: Insulation resistance after humidification 10 ⁹ Ω or less, copper migration

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 applied to the entire surface of a copper through-hole printed circuit board on which a pattern is formed by screen printing using a 100 mesh polyester screen so as to have a thickness of 20 to 30 μm. Was dried using a hot air dryer at 80 ° C for 30 minutes, then a negative film having a resist pattern was brought into close contact with the coating film, and an ultraviolet light exposure device (Model HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.) was used. Then, irradiate with ultraviolet rays (exposure amount eOOmjZcm ² ), develop with a 1% by mass aqueous solution of sodium carbonate for 60 seconds, and spray pressure of Okg Zcm ² , and then heat cure with a hot air dryer at 150 ° C for 60 minutes. No, a test substrate was made.

[0194] The test substrate having the obtained cured film was subjected to crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, electroless resistance according to the test methods and evaluation methods described above. A test for resistance to gold plating was conducted.

[0195] Also, a printed circuit board specified by the IPC instead of a copper through-hole printed wiring board

Using a B pattern (thickness 1.6 mm), a test substrate was fabricated under the same conditions as above, and an electrical insulation resistance test was performed.

[0196] [Table 14]

Table 15 shows the results of the above tests.

[Table 15]

Replacement form (Rule 26) Practical example No.

1 6 1 7 1 8 1 9 20 F 8

fllj Nofujino 1 earth 'Ο ο o o o

〇 0 0 o 〇 o o

Acid resistant 〇 ο o 〇 o o o Alkali resistant

Sex ο ο ooo 〇 o no ¹ !

Plating resistance ο 0 o o o o o Electrical insulation

Resistance ο ο ° o o o o

[0198] As is clear from the results shown in Table 15, in Comparative Examples 7 and 8 in which a carboxyl group-containing photosensitive resin was used as the photosensitive component, the crack resistance during a heat cycle was inferior. In Examples 16 to 20 further containing the tetra (meth) acrylate conjugate according to the above, the cracking resistance was excellent.

Industrial applicability

As described above, the (meth) atalylate compound of the present invention and the hardening composition containing the same are excellent in photocurability and Z or heat curability, and are resistant to moisture absorption. In addition, since a hardened product excellent in heat resistance and flexibility under high humidity can be obtained, it can be used for various applications such as resist ink, paint, and molding material.

[0200] In addition to the tetra (meth) atalylate toy conjugate (B) of the present invention, an alkali-soluble lipoxyl group-containing tie (A), a polymerization initiator (C), and a diluent A curable composition containing a solvent (D), a compound (E) having two or more cyclic ethers in one molecule, a curing catalyst (F), etc. has excellent photocurability and Z or heat curability, and Even when exposed to high and low temperatures, cracks occur in the hardened film, and it is possible to obtain a cured product with excellent properties as described above. Resist, plating resist, interlayer insulating layer of multilayer wiring board, permanent mask used for manufacturing tape carrier package, resist for flexible wiring board, resist for color filter,

Replacement Form (Rule 26) ' It is useful for applications such as dry film of the above resist and ink jet printing of the above resist. ·.

Claims

The scope of the claims

[1] A tetra (meth) acrylate conjugate represented by the following general formula (1).

(However,

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

[2] The tetra (meth) atalylate compound according to claim 1, wherein the dicarboxylic acid residue X is an aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue.

[3] The tetra (meth) acrylate according to claim 1, wherein the dicarboxylic acid residue X is an aromatic dicarboxylic acid residue represented by the following formulas (B1) and (B7). Dagger.

[Formula 2]

(Where R \ R ² R ³ R ⁴ represents a hydrogen atom or a methyl group.)

Replacement form (Rule 26)

[4] A cured product of the tetra (meth) acrylate conjugate according to any one of claims 1 to 3.

[5] A curable composition comprising a tetra (meth) atalylate compound represented by the following general formula (1).

[Formula 3]

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

6. 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.

[7] 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).

[Formula 4]

Difference form (parent regulation 26) (However, R \ R ² , R ³ and R ⁴ represent a hydrogen atom or a methyl group.)

[8] The hard fibrous yarn composition according to any one of claims 5 to 7, further comprising another radical polymerizable monomer and Z or a polymerization initiator.

[9] A cured product of the curable composition according to any one of claims 5 to 8.

[10] The cured product according to claim 9, which contains a fiber reinforcing material.

[11] It is necessary to contain (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 diluting solvent. Characteristic curable composition. .

[Formula 5]

CH ₂ = C— C— 0— CH ₂ \ o 0 ₇ CH ₂ -0-C -C = CH ₂

CH-O-C-X-C-O-CH (1)

CH ₂ = C -CO-CHj ^{7 X} CH ₂ -0-C -C = CH,

R ² 0 0

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

12. 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.

[13] The 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). .

[Formula 6]

Replacement form (Chief rule 26)

(However, RRRR ⁴ represents a hydrogen atom or a methyl group.)

14. 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.

[15] The curable composition according to any one of claims 11 to 14, further comprising (F) a hardening catalyst.

[16] The method according to claims 11 to, further comprising (G) another radical polymerizable monomer.

15. The curable composition according to any one of item 15 to item 15.

[17] A cured product of the curable composition according to any one of claims 11 to 16.

Replacement form (Rule 26)