JP2014012755A - Novel epoxy carboxylate compound, derivative thereof, active energy ray=curable resin composition containing the same and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition that gives a cured film excellent in curability, flexibility, toughness and electric reliability.SOLUTION: The active energy ray-curable resin composition comprises: a reactive epoxy carboxylate compound (A) produced by reacting an epoxy resin (a) produced by reacting an epoxy resin (X) having a glycidyl phenyl ether-octahydrometanoindene as a repeating structure and a phenol resin (Y) having a phenol-octahydrometanoindene as a repeating structure and having 2<Mw/Mn<20 with a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule and a carboxylic acid compound (c) having both a hydroxyl group and a carboxyl group in one molecule; or a reactive polycarboxylic acid compound (B) produced by reacting the reactive epoxy carboxylate compound (A) with a polybasic acid anhydride.

Description

  The present invention comprises reacting an epoxy resin (a) having a polycyclic hydrocarbon group having a specific structure with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. It is related with the reactive epoxycarboxylate compound (A) obtained by this, the reactive polycarboxylic acid compound (B) which is the acid modification thing, the active energy ray hardening-type resin composition containing them, and its hardened | cured material.

  Printed wiring boards are required to have higher precision and higher density in order to reduce the size and weight of portable devices and improve communication speed. With this, the demand for solder resist that covers the circuit itself of the wiring board is becoming increasingly sophisticated. Therefore, there is a demand for heat resistance and thermal stability that are higher than conventional requirements, as well as high reliability, that is, performance that can withstand high-temperature and high-humidity conditions and thermal shock.

  Patent Document 1 describes an acid-modified epoxy acrylate compound having an epoxy resin having a polycyclic hydrocarbon group as a basic skeleton and a cured product thereof, and is also known to have relatively high toughness after curing. It has been. A solder resist using the same is also described. Although this solder resist has a relatively high reliability, it does not satisfy the higher reliability required in recent years with the digitization of transportation equipment and the like.

  Patent Document 2 and the like describe an epoxy carboxylate compound obtained by reacting a general epoxy resin with a carboxylic acid compound having acrylic acid and a hydroxyl group, and has excellent developability while having a low acid value. Further, it is described that this compound has resist ink suitability, but the performance is insufficient.

  On the other hand, a resin composition comprising a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and the like has been used as a display device material.

In recent years, materials for display devices such as “LCD, EL, PDP, FED (SED), rear projection display, electronic paper, digital camera, etc., especially display elements, materials around display elements” Color liquid crystal displays (LCDs) are rapidly spreading. In general, a color liquid crystal display device has a structure in which a color filter and an electrode substrate such as a TFT substrate are opposed to each other to provide a gap of about 1 to 10 μm, a liquid crystal compound is filled in the gap and the periphery is sealed with a sealing material. Have taken.
The color filter includes a black matrix layer formed in a predetermined pattern on the transparent substrate to shield the boundary between pixels, and usually red (R), green (G), A colored layer in which blue (B) is arranged in a predetermined order, a protective film, and a transparent electrode film are stacked in this order from the side close to the transparent substrate. An alignment film is provided on the inner surface side of the color filter and the electrode substrate facing the color filter. Further, in the gap, in order to maintain a uniform and uniform cell gap between the color filter and the electrode substrate, pearls having a constant particle diameter are dispersed as spacers, or columns or stripes having a height corresponding to the cell gap. A spacer is formed. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind each pixel colored in each color. Such color filters are used not only in color liquid crystal display devices but also in other display devices such as EL and rear projection displays.

  The colored layer, the protective film, and the spacer can be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each color pixel. The protective film is preferably one that can cover only the region where the colored layer is formed on the transparent substrate in consideration of the adhesion and sealing property of the seal portion. In addition, it is necessary to accurately provide the spacer in the black matrix layer forming region, that is, in the non-display region. For this reason, a colored layer, a protective film, and a columnar spacer have been formed using a curable resin that can easily limit a region to be cured by a photomask.

  In addition, in order to form a colored layer, a protective film, or a columnar spacer, development using an organic solvent after exposing the coated surface of the curable resin is complicated in terms of handling and waste liquid treatment, and economical. Therefore, a curable resin has been developed in which an acidic group is introduced into the curable resin so that it can be developed with an aqueous alkaline solution after exposure. These applications require a high temperature (200-260 ° C. or higher) when forming an alignment film and a transparent electrode, so that they have very high heat resistance, especially color resists and spacers. There is a need for excellent products.

  In addition, as described above, in recent years, it is necessary to accurately provide the black matrix layer in the formation region, that is, in the non-display region. It has become the target. This spacer is required to have mechanical strength and heat resistance that can withstand high temperature and high pressure in a panel sealing step after liquid crystal injection when manufacturing a display panel (Patent Document 3).

As the photosensitive resin as described above, an alkali-soluble photosensitive resin is used, which has an advantage that the amount of the carboxyl group and the radically polymerizable (meth) acryloyl group can be freely adjusted. Various resin skeletons have been proposed as such resins.
Patent Document 4 describes a photosensitive coloring composition containing a binder resin obtained by further reacting a reaction product of a dicyclopentadiene-phenol condensed epoxy resin and an unsaturated group-containing carboxylic acid with a polybasic acid anhydride. It has excellent liquid stability, heat resistance, adhesion to the substrate, and edge shape. However, it is inferior in pigment dispersibility, sensitivity, and developability and is not at a sufficiently satisfactory level.

Japanese Patent Laid-Open No. 5-214048 JP-A-6-324490 Japanese Patent Laid-Open No. 2002-40440 JP 2004-295084 A

  The present invention improves the above-mentioned problems of the prior art, gives a cured film excellent in curability, flexibility, toughness, and electrical reliability, and requires a hard coat material and a resist that requires flexibility capable of alkali development. To provide a novel epoxy carboxylate compound suitable as a material, printing ink that requires good pigment dispersibility, a color resist, a black matrix material for LCD, a derivative thereof, and an active energy ray-curable resin composition containing the compound With the goal.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

（式中ｎは繰り返し数を表す。）
で表されるエポキシ樹脂であり、フェノール樹脂（Ｙ）が下記式（２）

（式中ｎは繰り返し数を表す。）
で表されるフェノール樹脂である上記（１）記載の反応性エポキシカルボキシレート化合物（Ａ）
（５）上記（１）〜（４）のいずれか１項に記載の反応性エポキシカルボキシレート化合物（Ａ）に多塩基酸無水物（ｃ）を反応させて得られる反応性ポリカルボン酸化合物（Ｂ）
（６）上記（１）〜（４）のいずれか１項に記載の反応性エポキシカルボキシレート化合物（Ａ）及び／又は上記（５）に記載の反応性ポリカルボン酸化合物（Ｂ）を含む活性エネルギー線硬化型樹脂組成物
（７）反応性エポキシカルボキシレート化合物（Ａ）及び反応性ポリカルボン酸化合物（Ｂ）以外の反応性化合物（Ｃ）を含む上記（６）に記載の活性エネルギー線硬化型樹脂組成物
（８）光重合開始剤を含む上記（６）又は（７）に記載の活性エネルギー線硬化型樹脂組成物
（９）着色顔料を含む上記（６）〜（８）のいずれか１項に記載の活性エネルギー線硬化型樹脂組成物
（１０）成形用材料である上記（６）〜（９）のいずれか１項に記載の活性エネルギー線硬化型樹脂組成物
（１１）皮膜形成用材料である上記（６）〜（９）のいずれか１項に記載の活性エネルギー線硬化型樹脂組成物
（１２）レジスト材料組成物である上記（６）〜（１１）のいずれか一項に記載の活性エネルギー線硬化型樹脂組成物
（１３）上記（６）〜（１２）のいずれか一項に記載の活性エネルギー線硬化型樹脂組成物の硬化物。
（１４）上記（１１）に記載の活性エネルギー線硬化型樹脂組成物の硬化物でオーバーコートされた物品
に関する。 That is, the present invention
(1) Epoxy resin (X) having a repeating structure in which two glycidyl phenyl ethers are bonded with an octahydromethanoindene structure as a linker and two phenols are bonded with an octahydromethanoindene structure as a linker An epoxy resin obtained by reacting a phenol resin (Y) having a repeating structure with a segment, wherein the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 <Mw / Mn <20. Obtained by reacting an epoxy resin (a) with a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule and a carboxylic acid compound (c) having both a hydroxyl group and a carboxy group in one molecule. Reactive epoxycarboxylate compound (A)

(2) Epoxy equivalent is 290 to 1000 g / eq. The reactive epoxycarboxylate compound (A) according to the above (1) using the epoxy resin (a)
(3) Reactive epoxycarboxylate compound (A) according to (1) above, wherein the epoxy resin (a) according to (1) above has a viscosity at 200 ° C. of 0.1 to 20 Pa · s.
(4) Epoxy resin (X) is represented by the following formula (1)

(In the formula, n represents the number of repetitions.)
The phenol resin (Y) is represented by the following formula (2):

(In the formula, n represents the number of repetitions.)
The reactive epoxycarboxylate compound (A) described in (1) above, which is a phenol resin represented by
(5) Reactive polycarboxylic acid compound obtained by reacting the reactive epoxycarboxylate compound (A) according to any one of (1) to (4) above with a polybasic acid anhydride (c) ( B)
(6) Activity including the reactive epoxycarboxylate compound (A) described in any one of (1) to (4) above and / or the reactive polycarboxylic acid compound (B) described in (5) above. Energy ray curable resin composition (7) Active energy ray curable according to (6) above, comprising a reactive compound (C) other than the reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B) (8) The active energy ray-curable resin composition according to the above (6) or (7) containing a photopolymerization initiator (8) Any of the above (6) to (8) containing a colored pigment Active energy ray-curable resin composition according to item 1 (10) Active energy ray-curable resin composition according to any one of the above (6) to (9), which is a molding material, (11) Film formation (6) to (9) which are materials for use The active energy ray-curable resin composition according to any one of (6) to (11) above, which is a resist material composition (12) 13) A cured product of the active energy ray-curable resin composition according to any one of (6) to (12) above.
(14) The present invention relates to an article overcoated with a cured product of the active energy ray-curable resin composition according to (11).

  The active energy ray-curable resin composition containing the reactive epoxycarboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention not only obtained a tough cured product but also dried the solvent. Even in such a state, the resin has excellent physical properties. In addition, a cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays has thermal and mechanical toughness, good storage stability, and high temperature and high temperature. It can be suitably used for a film-forming material having high reliability that can withstand moisture and cold shock.

  The active energy ray-curable resin composition of the present invention is preferably a solder resist for a printed wiring board, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, plating, for example, which requires particularly high reliability. It can be used for applications such as resists and photosensitive optical waveguides.

  Furthermore, it has a high affinity with colored pigments such as carbon black, and can exhibit good developability even at high pigment concentrations, and resist materials for color resists, color filters, especially black matrix materials, etc. Also, it can be suitably used.

  Hereinafter, the present invention will be described in detail.

  In the active energy ray-curable resin composition of the present invention, the epoxy resin (a), which is an essential component, is a segment in which two glycidyl phenyl ethers are bonded with an octahydromethanoindene structure (also referred to as a tricyclodecyl structure) as a linker. An epoxy resin (X) having a repeating structure and two phenols are obtained by reacting a phenol resin (Y) having a repeating structure with a segment in which an octahydromethanoindene structure is bonded as a linker. The phenolic resin (Y) is a phenolic resin obtained by reacting dicyclopentadiene with phenol. The epoxy resin obtained by epoxidizing this resin is generally sold as an XD manufactured by Nippon Kayaku Co., Ltd. -1000 series, Dainippon Ink & Chemicals, Inc. HP-7200 series, etc. are mentioned. The epoxy resin (a) is an epoxy resin having a wide molecular weight distribution and has high toughness even when compared with these product groups.

  The epoxy resin (a) in the present invention has a portion in which two phenylene groups or glycidoxyphenylene groups are bonded using a dioxypropanol group as a linker. Such a bond is generally a bond formed when a high molecular weight grade bisphenol A type epoxy resin (or phenoxy resin) is synthesized, and the synthesis method is also called a fusion method (advanced method or two-step method). (See pages 24-25 and 30-31, edited by Hiroshi Kakiuchi). The epoxy resin (a) is a compound obtained by utilizing this fusion method.

（式中ｎは繰り返し数を表し、通常１〜１０である。） The epoxy resin (X) which is a raw material of the epoxy resin (a) is not particularly limited as long as it has the above structure, but usually the phenol resin (Y) and epihalohydrin are reacted in the presence of an alkali metal hydroxide. Thus, an epoxy resin having a narrow molecular weight distribution width (Mw (weight average molecular weight) / Mn (number average molecular weight) is about 2.0 or less) is obtained. In addition, the said epoxy resin (X) can also use the said commercially available epoxy resin. The epoxy resin (X) is usually represented by the following formula (1).

(In the formula, n represents the number of repetitions and is usually 1 to 10.)

  In the reaction for obtaining the epoxy resin (X), epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, and the like can be used as the epihalohydrin, and epichlorohydrin which is easily available industrially is preferred in the present invention. The usage-amount of epihalohydrin is 3.0-20.0 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin (Y) as described above, Preferably it is 3.5-10.0 mol.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are distilled off continuously under reduced pressure or normal pressure, and the solution is further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol resin (Y), Preferably it is 0.95-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mol of the hydroxyl group of the phenol resin (Y).

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol resin (Y) used for epoxidation. . The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin (X).

（式中ｎは繰り返し数を表し、通常１〜１０である。） Next, an epoxy resin (a) can be obtained by reacting the epoxy resin (X) with the phenol resin (Y). In this method, the molar ratio of the glycidoxy group of the epoxy resin (X) and the hydroxyl group of the phenol resin (Y) is a factor that determines the introduction rate of the dioxypropanol group. The phenol resin (Y) is usually represented by the following formula (2).

(In the formula, n represents the number of repetitions and is usually 1 to 10.)

  The reaction between the epoxy resin (X) and the phenol resin (Y) uses a catalyst as necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; triphenylphosphine, diphenylphosphine Organic phosphines such as fin and tributylphosphine; Metal compounds such as tin octylate; Tetra-substituted phosphonium / tetra-substituted borate such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. The amount of these catalysts used is generally 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm, based on the total resin amount, although it depends on the type of the catalyst. In this reaction, since the reaction proceeds without adding a catalyst, it is desirable to use it appropriately according to the preferred reaction temperature and amount of the reaction solvent.

In this fusion method, a solvent may or may not be used. When a solvent is used, any solvent can be used as long as it does not affect the reaction. For example, the following solvents can be used.
Polar solvents, ethers: dimethyl sulfoxide, N, N′-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, diglyme, triglyme, propylene glycol monomethyl ether, etc.
Ester-based organic solvents: ethyl acetate, butyl acetate, butyl lactate, γ-butyrolactone, etc.
Ketone organic solvent: Methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other aromatic organic solvents: toluene, xylene, etc. The amount of the solvent used is 0 to 300% by weight, preferably 0 to 100% by weight based on the total resin weight. %.

  The reaction temperature and time are affected by the resin concentration and the catalyst amount, and the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. In view of productivity, the reaction time is preferably short, and the reaction temperature is 0 to 250 ° C, preferably 30 to 200 ° C. Therefore, the resin concentration and the catalyst amount are appropriately adjusted so that the reaction can be performed at a preferable time and temperature.

  Since the epoxy resin (a) has a dioxypropanol group, its hydroxyl equivalent becomes small. Specifically, the hydroxyl equivalent is 5000 or less. The hydroxyl equivalent can be calculated from the hydroxyl equivalent (measured in accordance with JIS K 0070) of the phenol-modified epoxy resin obtained by adding equimolar amount of phenol to the epoxy equivalent of the epoxy resin and the epoxy equivalent of the epoxy resin. .

The epoxy resin (a) has a wide molecular weight distribution. Usually, gel permeation chromatography is used as an index of the molecular weight distribution, and the value of Mw (weight average molecular weight) / Mn (number average molecular weight) is adopted. The Mw / Mn of a normal epoxy resin (X) is While it is less than 2.0, the epoxy resin (a) is usually 2.0 or more. A preferred range is 2 <Mw / Mn <20, preferably 2.5 <Mw / Mn <15. When Mw / Mn exceeds 20, the resin is in a gel-like state and not only has a high melt viscosity but also a low solubility in a solvent, which is inconvenient to handle. Adjustment of Mw / Mn can be appropriately performed according to the reaction ratio of the epoxy resin (X) and the phenol resin (Y) and the molecular weight thereof. For example, as the amount of the phenol resin (Y) with respect to the epoxy resin (X) is increased, the molecular weight becomes larger, and when the average molecular weight of the epoxy resin (X) and the phenol resin (Y) to be used is larger, the molecular weight distribution is more likely. And the Mw / Mn can be increased.
The epoxy resin (a) is a resin having a three-dimensional structure because the oxyglycidyl group of the epoxy resin (X) reacts with the phenolic hydroxyl group of the phenol resin (Y) in a network form.

The softening point of the epoxy resin (a) is preferably one having a softening point of 50 ° C. or more from the viewpoint of handling. A preferred range is 50 to 150 ° C, more preferably 75 to 140 ° C. When the softening point is 150 ° C. or higher, not only the melt viscosity is high but also the solubility in the solvent is low, which is inconvenient to handle. The melt viscosity is preferably 10 Pa · s or less at 200 ° C. When it is more than this, it is not only difficult to take out from the production container, but it can not be generally said, but when diluting with a solvent to make an epoxy resin varnish and making something like a prepreg, the varnish is applied to the glass cloth. After the impregnation, the prepreg is obtained by distilling off the solvent. At this time, the molding material may be adversely affected, for example, the escape of the solvent may be worsened. The softening point can be adjusted as appropriate depending on the reaction ratio of the epoxy resin (X) and the phenol resin (Y) and their molecular weight. For example, the softening point increases as the amount of the phenol resin (Y) with respect to the epoxy resin (X) increases.
In the reaction for obtaining the epoxy resin (a), the ratio of the epoxy resin (X) to the phenol resin (Y) is usually 1 mol of the epoxy group of the epoxy resin (X). An amount of 0.05 to 0.5 mol, preferably 0.076 to 0.356 mol is used.

  Next, the carboxylation step for the purpose of giving the carboxylate compound reactivity and obtaining the reactive epoxycarboxylate compound (A) of the present invention will be described.

  In this reaction, a reactive carboxylate compound (A) is obtained by reacting an epoxy resin (a) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and one or more carboxyl groups.

  The carboxylic acid compound (b) shown here is reacted for imparting reactivity to active energy rays. Specific examples include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. Monocarboxylic acid compound containing one carboxyl group in one molecule, (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and half-esters which are equimolar reactants, saturated or unsaturated dibasic acid and plural Carboxyl group in one molecule such as half-esters that are equimolar reaction products with glycidyl (meth) acrylate derivatives having an epoxy group of And polycarboxylic acid compounds having a plurality of.

  Of these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), (b) is preferably a monocarboxylic acid, even when the monocarboxylic acid and the polycarboxylic acid are used in combination. The value represented by the molar amount of monocarboxylic acid / the molar amount of polycarboxylic acid is preferably 15 or more.

  Most preferably, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is used from the viewpoint of sensitivity when an active energy ray-curable resin composition is used.

  The charging ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this reaction should be appropriately changed according to the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as a reactive carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

  On the other hand, by reducing the charged amount of the carboxylic acid compound and leaving the unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, the polymerization reaction or thermal polymerization reaction by the photocationic catalyst. Can be used in combination. In this case, however, attention should be paid to the storage of the reactive carboxylate compound and the examination of the production conditions.

  When manufacturing the reactive epoxy carboxylate compound (A) which does not leave an epoxy group, it is preferable that a carboxylic acid compound (b) is 90-120 equivalent% with respect to 1 equivalent of epoxy resins (a). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound charged is larger than this, an excess of the carboxylic acid compound (b) remains, which is not preferable.

  Moreover, when leaving an epoxy group, it is preferable that a carboxylic acid compound (b) is 20-90 equivalent% with respect to 1 equivalent of epoxy resins (a). When deviating from this range, the effect of the composite curing is reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability with time of the carboxylate compound (A).

  Carboxylation reaction can also be made to react without solvent, or can be diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

  The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and intended use of the resin obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight based on the solid content. used.

  Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

  Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, and triethylene. Mono, such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as And the like.

  Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Examples include ethers and cyclic ethers such as tetrahydrofuran.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, the reaction can be performed in a single or mixed organic solvent such as other reactive compounds (C) described later. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  In the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is a reaction in which a reaction product, that is, an epoxy resin (a), a carboxylic acid compound (b), and optionally a solvent or the like is added. It is 0.1-10 weight part with respect to the total amount of a thing. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling appropriately.

  A preferable molecular weight range of the reactive epoxycarboxylate compound (A) thus obtained is a polystyrene-reduced weight average molecular weight in GPC of 1,000 to 50,000, more preferably 2,000 to 30,000. It is.

  When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is larger than this, the viscosity becomes high and coating or the like becomes difficult.

  Next, the acid addition step will be described in detail. The acid addition step is performed for the purpose of obtaining a reactive polycarboxylic acid compound (B) by introducing a carboxyl group into the reactive carboxylate compound obtained in the previous step as necessary. That is, a carboxyl group is introduced through an ester bond by adding a polybasic acid anhydride (c) to a hydroxyl group generated by a carboxylation reaction.

  As specific examples of the polybasic acid anhydride (c), for example, any compound having an acid anhydride structure in the molecule can be used, but it is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance and the like. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Is particularly preferred.

  The reaction for adding the polybasic acid anhydride (c) can be performed by adding the polybasic acid anhydride (c) to the carboxylation reaction solution. The amount added should be changed as appropriate according to the application.

  For example, when the polycarboxylic acid compound (B) of the present invention is used as an alkali development type resist, the polybasic acid anhydride (c) is finally added. Calculation that the solid content acid value (based on JISK5601-2-1: 1999) of the obtained reactive polycarboxylic acid compound (B) is 40 to 120 mg · KOH / g, more preferably 60 to 110 mg · KOH / g. It is preferable to charge the value. When the solid content acid value at this time is within this range, the aqueous alkaline resin developability of the photosensitive resin composition of the present invention exhibits good developability. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  In the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction product, that is, an epoxy compound (a), a carboxylate compound obtained from the carboxylic acid compound (b), and a large amount. It is 0.1-10 weight part with respect to the total amount of the reaction material which added the basic acid anhydride (c) and the solvent etc. depending on the case. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples include zirconium acid.

  This acid addition reaction can be reacted with no solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. In addition, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can. The solvent that can be used may be the same as that used in the carboxylation reaction.

  The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and intended use of the resin obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight based on the solid content. Used.

  In addition, the reaction can be performed in a single or mixed organic solvent such as the reactive compound (C). In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor.

In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

  Specific examples of the reactive compound (C) that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. Can be mentioned.

  Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy) Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (C) is most preferably an acrylate that is radically curable. In the case of the cationic type, the carboxylic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.

  The active energy ray-curable resin composition of the present invention is prepared by mixing the reactive epoxycarboxylate compound (A) or the reactive polycarboxylic acid compound (B) of the present invention with another reactive compound (C). Can be obtained. At this time, you may add another component suitably according to a use.

  The active energy ray-curable resin composition of the present invention is 97 to 5 parts by weight, preferably 87 to 10 parts by weight of the reactive epoxycarboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) in the composition. Parts, other reactive compounds (C) 3 to 95 parts by weight, more preferably 3 to 90 parts by weight. If necessary, other components may be contained in an amount of 0 to 80 parts by weight.

  The carboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the active energy ray-curable resin composition of the present invention can be appropriately used depending on the application. For example, the reactive epoxy carboxylate compound (A) is used in the case of the so-called solvent development type in which a pattern is formed by a printing method or unreacted sites are washed away by a solvent or the like without developing even in the same solder resist application. In the case of developing with alkaline water, the reactive polycarboxylic acid compound (B) is used. In general, the reactive polycarboxylic acid compound (B) is often used for this application from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if (A) and (B) are used in combination.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The colored pigment used in the present invention is used for using the active energy ray resin composition of the present invention as a coloring material. Since the balance between the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is in a specific range, particularly excellent dispersibility of the pigment, that is, dispersibility is exhibited.

  Although this mechanism is not clear, since the dispersion proceeds well, the pigment concentration can be increased as a result, and in a composition that requires development, the dispersion is in a more favorable state. Good patterning characteristics are exhibited, and there are few development residues in the development and dissolution area, which is preferable.

  Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.

  In the present invention, the molding material refers to an uncured composition put into a mold, or a mold is pressed to form an object, and then a curing reaction is caused by active energy rays to form, or an uncured composition. It refers to a material used for applications in which a focus reaction such as laser is irradiated to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. Such materials include adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, a film-forming material is temporarily applied to a peelable substrate to form a film, and then a so-called dry film in which a film is formed by being bonded to the originally intended substrate also corresponds to the film-forming material. .

  The present invention also includes a cured product obtained by irradiating the photosensitive resin composition with active energy rays, and also includes a multilayer material having a layer of the cured product.

  Among these, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (B) increases the adhesion to the substrate, and therefore, it is preferably used as an application for coating a plastic substrate or a metal substrate.

  Furthermore, taking advantage of the feature that the unreacted reactive polycarboxylic acid compound (B) is soluble in an alkaline aqueous solution, it is also preferable to use it as an alkaline water developable resist material composition.

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, it is a composition used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or unirradiated part with, for example, a solvent or an alkaline solution and drawing.

  The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful for solder resist materials, interlayer insulating materials for build-up methods, and optical waveguides. It is also used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.

  As a particularly suitable application, taking advantage of the property that a tough cured product can be obtained, making use of a permanent resist application such as a solder resist, and the property of good pigment dispersibility, printing inks, color filters, etc. The use of a color resist, particularly a black matrix resist is preferred.

  Patterning using the photosensitive resin composition of the present invention can be performed, for example, as follows. The composition of the present invention is applied on the substrate with a film thickness of 0.1 to 200 μm by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating. Is dried at a temperature of usually 50 to 110 ° C., preferably 60 to 100 ° C., whereby a coating film can be formed. Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm 2 through a photomask having an exposure pattern, and using a developer described later, for example, spraying, vibration A desired pattern can be obtained by dipping, paddle, brushing or the like.

  Examples of the alkaline aqueous solution used for the development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, and tetramethylammonium hydroxide. Organic alkali aqueous solutions such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  In addition, it is particularly suitably used as a dry film application that requires mechanical strength before the curing reaction with active energy rays. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive carboxylate compound of the present invention has a relatively high molecular weight, but is excellent. Developability can be exhibited.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with active energy rays.

  The article overcoated with the resin composition of the present invention is a material having at least two layers obtained by forming and curing the active energy ray-curable resin composition shown in the present invention on a substrate. Indicates.

  In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, other components may be added to the composition up to 70 parts by weight. Examples of other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine-based initiator, borate-based initiator, And other photoacid generators.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). And triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide). The phosphonium salt of acetic acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  Other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (TrigonalPI, etc., manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl) Etanone (Sandray 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.) and the like can be mentioned. Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2,4 -Trichloromethyl- (4'-methoxystyryl) -6-triazine (such as TriazinePMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as TriazinePP manufactured by Panchim), 2,4-trichloro Methyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (Sanwa) 2) (2'-furylethylidene)- , 3,6-Bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

  Examples of the borate photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye, and other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl). ) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurokin Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical) V50, etc. manufactured by the same company), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [Eta-5-2-4- (cyclopentadecyl) (1 , 2,3,4,5,6, eta)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261 manufactured by CibaGeigy, etc.), bis (y5- Cyclopentadienyl) bis [2,6-difluoro-3-(1H-pyr-1-yl) phenyl] titanium (CibaGeigy Co. CGI-784, etc.) and the like.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation An inhibitor or the like can be used.

  Further, as other pigment materials, for example, those not intended for coloring, so-called extender pigments can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  In addition to this, as resins not showing reactivity to active energy rays (so-called inert polymers), for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the resin composition in the range of up to 40 parts by weight.

  In particular, when the reactive polycarboxylic acid compound (B) is to be used for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. This is because the carboxyl group derived from (B) remains even after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger cross-linked structure. The cation-reactive monomer can be used as the known general epoxy resin.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added to the resin composition in a range of 50 parts by weight, more preferably up to 35 parts by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows a mass part.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JISK7236: 2001.
2) Softening point: Measured by a method according to JISK7234: 1986.
3) Acid value: measured by a method according to JISK0070: 1992. 4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 ° C
Detector: RI (differential refractometer)
Molecular weight standard: polystyrene

Synthesis Example 1: Synthesis Synthesis Example 1-1 of Epoxy Resin
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 187 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 13 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added, washed with water, and 198 parts of the desired epoxy resin (EP1) was obtained by distilling off the solvent under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin is 290 g / eq. The softening point was 92 ° C. and the melt viscosity (200 ° C.) was 0.10 Pa · s. The value of Mw / Mn was 2.1.

Synthesis Example 1-2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value of 1.95) 185 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 15 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added and washed with water, and the resulting solution was distilled off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator to obtain 198 parts of the desired epoxy resin (EP2). It was. The epoxy equivalent of the obtained epoxy resin is 303 g / eq. The softening point was 96 ° C. and the melt viscosity (200 ° C.) was 0.13 Pa · s. The value of Mw / Mn was 2.8.

Synthesis Example 1-3
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 183 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 17 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added and washed, and the resulting solution was 198 parts of the desired epoxy resin (EP3) by distilling off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin was 310 g / eq. The softening point was 99 ° C. and the melt viscosity (200 ° C.) was 0.18 Pa · s. The value of Mw / Mn was 3.5.

Synthesis Example 1-4
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 180 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 20 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added and washed, and the resulting solution was 198 parts of the desired epoxy resin (EP4) by distilling off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin was 342 g / eq. The softening point was 102 ° C. and the melt viscosity (200 ° C.) was 0.26 Pa · s. The value of Mw / Mn was 4.8.

Synthesis Example 1-5
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 170 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 30 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added, washed with water, and the resulting solution was distilled off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator to obtain 198 parts of the desired epoxy resin (EP5). It was. The epoxy equivalent of the obtained epoxy resin is 419 g / eq. The softening point was 117 ° C. and the melt viscosity (200 ° C.) was 0.94 Pa · s. The value of Mw / Mn was 8.3.

Synthesis Example 1-6
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 165 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 35 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added and washed with water, and the resulting solution was 198 parts of the desired epoxy resin (EP6) by distilling off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin is 473 g / eq. The softening point was 120 ° C. and the melt viscosity (200 ° C.) was 1.8 Pa · s. The value of Mw / Mn was 18.

Comparative Synthesis Example 1-1
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value is 1.95) 190 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 10 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added, washed with water, and the resulting solution was 198 parts of the desired epoxy resin (EP7) by distilling off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin was 288 g / eq. The softening point was 88 ° C. and the melt viscosity (200 ° C.) was 0.06 Pa · s. The value of Mw / Mn was 1.99.

Comparative Synthesis Example 1-2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, epoxy resin (X) (Nippon Kayaku Co., Ltd. XD-1000 epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn The value of 1.95) is 160 parts, phenol resin (Y) (Shin Nippon Oil Co., Ltd. DPP-6095L hydroxyl equivalent 178 g / eq. Average functional group number 2.2) 40 parts, toluene 50 parts, tetramethylammonium chloride 0. Two parts were added and reacted at 120 ° C. for 4 hours. After completion of the reaction, 300 parts of toluene was added and washed, and the resulting solution was 198 parts of the desired epoxy resin (EP8) by distilling off the solvent and the like under reduced pressure at 180 ° C. using a rotary evaporator. It was. The epoxy equivalent of the obtained epoxy resin is 551 g / eq. The softening point was 126 ° C. and the melt viscosity (200 ° C.) was 3.0 Pa · s. The value of Mw / Mn was 26.

Example 1 Preparation of Epoxy Carboxylate Compound (A) Epoxy resins (a) prepared in Synthesis Examples 1-1, 1-2, 1-3, 1-4, 1-5, 1-6 are described in the table. Amount of acrylic acid (abbreviation AA, Mw = 72) as a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule, triphenylphosphine as a catalyst 3 g of propylene glycol monomethyl ether monoacetate as a solvent was added to a solid content of 80% and reacted at 100 ° C. for 24 hours to obtain an epoxy carboxylate compound (A) solution.

Comparative Example 1: Preparation of comparative epoxycarboxylate compound XD-1000 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 254 g / eq. Average functional group number 2.5 Mw / Mn is 1.95), Comparative Synthesis Example 1 Each of the epoxy resins prepared in 1 and 1-2 is described in the table, and acrylic acid (abbreviation AA, abbreviation AA, as a compound (b) having both one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule. Mw = 72) is added in the amount shown in the table, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent so as to have a solid content of 80%, and reacted at 100 ° C. for 24 hours to obtain an epoxy carboxylate compound (A) A solution was obtained.

The reaction end point was determined by the solid content acid value (AV: mgKOH / g), and the measured values are shown in Table 1. The acid value was measured with a reaction solution and converted into an acid value as a solid content. Further, the molecular weight was measured by GPC, and the weight average molecular weight is shown in Table 1.

注）ＡＡのエポキシ樹脂（ａ）に対するモル比はいずれも１．０である。

Note) The molar ratio of AA to the epoxy resin (a) is 1.0.

Example 2: Preparation of reactive polycarboxylic acid compound (B) Tetrahydrophthalic anhydride (abbreviated as THPA) was added as polybasic acid anhydride (c) to 297 g of the carboxylate compound (A) solution obtained in Example 1. Propylene glycol monomethyl ether monoacetate is added so as to have a solid content of 65 parts by weight as a solvent described in Table 2 and heated to 100 ° C., followed by acid addition reaction to obtain a reactive polycarboxylic acid compound (B) solution. It was. The solid content acid value (AV: mgKOH / g) and the weight average molecular weight are shown in Table 2.

Example 3: Preparation of hard coat composition 20 g of the epoxycarboxylate compound (A) synthesized in Example 1, 4 g of dipentaerythritol hexaacrylate, which is a radically curable reactive compound (C), and an ultraviolet reactive initiator. As a result, 1841.5 g of Irgacure was dissolved by heating.
Further, this was coated on a polycarbonate plate by a hand applicator so as to have a film thickness of 20 microns at the time of drying, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, an ultraviolet-ray exposure apparatus (manufactured by Oak Seisakusho) equipped with a high-pressure mercury lamp was irradiated with an ultraviolet ray with an irradiation dose of 1000 mJ and cured to obtain an article overcoated with the resin composition.
The hardness of the coating film of the article overcoated with this resin composition was measured according to JISK5600-5-4: 1999, and an impact test was conducted according to ISO6272-1: 2002.
Impact resistance test ○: No scratch or peeling
Δ: Slightly scratched
X: peeling

  As is clear from the above results, the hard coat composition of the present invention has high impact properties and hardness.

Example 4: Preparation of dry film type resist composition 54.44 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and HX-220 (trade name: Nippon Chemical Co., Ltd.) as the other reactive compound (C) Yakugure 907 (manufactured by Ciba Specialty Chemicals) and 4.72 g of Kayacure DETX-S (Nihon Kayaku Co., Ltd.) .47 g, 14.83 g of GTR-1800 (manufactured by Nippon Kayaku) as the curing component, 1.05 g of melamine as the thermosetting catalyst, and 20.95 g of methyl ethyl ketone as the concentration adjusting solvent, kneaded with a bead mill and uniformly dispersed A resist resin composition was obtained.
The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. A polyethylene film to be a protective film was attached to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

  Next, in order to estimate the mask on which the circuit pattern was drawn and sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays. Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was heat-cured for 60 minutes with a hot air dryer at 150 ° C. to obtain a cured film.

Evaluation of cold thermal shock resistance A thermal shock test was performed on a polyimide printed board on which a cured resist film was formed in the range of −65 to 120 ° C. The test method was based on JISC5012-9.1: 1993. After completion of the test, a peel test using cellophane tape (registered trademark) was performed.
○: No peeling Δ: Slight peeling is observed.
X: peeling

Evaluation of high temperature and humidity resistance A polyimide printed circuit board on which a cured resist film was formed was placed in an autoclave at 120 ° C. for 1 hour. The substrate was taken out, allowed to air dry at room temperature, and then subjected to a peeling test using cellophane tape (registered trademark).
○: No peeling Δ: Slight peeling is observed.
X: peeling

Sensitivity evaluation Sensitivity was determined based on how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).

Evaluation of developability The developability was evaluated based on the so-called break time (unit: second) until the pattern shape portion was completely developed when developing the exposed portion that passed through the pattern mask.

Curability evaluation Curability evaluation was shown by pencil hardness of the cured film after heating at 150 ° C. The evaluation method was based on JISK5600-5-4: 1999.

  As is apparent from the above results, the resist composition in the present invention has high cold thermal shock resistance and high temperature and humidity resistance. Further, it has good developability and sensitivity as a resist.

Example 5 and Comparative Example 5: Pigment dispersibility 20 g of the polycarboxylic acid compound obtained in Example 2 or Comparative Example 2, respectively, and DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate) as the reactive compound (C) Monomer) 5.0 g, 10 g of propylene glycol monomethyl ether acetate as an organic solvent, and 10 g of Mitsubishi Carbon Black MA-100 as a color pigment were mixed and stirred. 35 g of glass beads were put there and dispersed for 1 hour with a paint shaker.
The dispersion after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried for 10 minutes with a hot air dryer at 80 ° C. The gloss of the coating film surface after the drying was measured using a 60 ° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of the carbon black. At this time, a higher gloss indicates better pigment dispersibility.

  As is clear from the above results, the dispersion containing the reactive polycarboxylic acid compound (B) in the present invention is excellent in pigment dispersibility.

  The active energy ray-curable composition of the present invention and the cured product thereof are hard coat materials and resist materials that require flexibility capable of alkali development as materials having both curability, flexibility, toughness, and flame retardancy. Suitable for applications that exhibit good pigment dispersibility, for example, active energy ray-curable printing inks, color resists, especially black matrix for LCD as a material having both resist dispersibility and developability resist suitability, etc. It can be used particularly preferably.

Claims (14)

Two glycidyl phenyl ethers repeat an epoxy resin (X) having a repeating structure with a segment bonded with an octahydromethanoindene structure as a linker, and two phenols repeat a segment with an octahydromethanoindene structure bonded as a linker An epoxy resin obtained by reacting a phenol resin (Y) having a structure, wherein the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 <Mw / Mn <20 It is obtained by reacting a) a compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule and a carboxylic acid compound (c) having both a hydroxyl group and a carboxy group in one molecule. Reactive epoxycarboxylate compound (A) characterized. Epoxy equivalent is 290 to 1000 g / eq. The reactive epoxycarboxylate compound (A) according to claim 1, wherein an epoxy resin (a) is used. The reactive epoxycarboxylate compound (A) according to claim 1, wherein an epoxy resin (a) having a viscosity at 200 ° C of 0.1 to 20 Pa · s is used. The epoxy resin (X) is represented by the following formula (1)

(In the formula, n represents the number of repetitions.)
The phenol resin (Y) is represented by the following formula (2):

(In the formula, n represents the number of repetitions.)
The reactive epoxycarboxylate compound (A) according to claim 1, which is a phenol resin represented by the formula: A reactive polycarboxylic acid compound (B) obtained by reacting the reactive epoxycarboxylate compound (A) according to any one of claims 1 to 4 with a polybasic acid anhydride (c). An active energy ray-curable resin composition comprising the reactive epoxycarboxylate compound (A) according to any one of claims 1 to 4 and / or the reactive polycarboxylic acid compound (B) according to claim 5. . The active energy ray-curable resin composition according to claim 6, comprising a reactive compound (C) other than the reactive epoxycarboxylate compound (A) and the reactive polycarboxylic acid compound (B). The active energy ray-curable resin composition according to claim 6 or 7, further comprising a photopolymerization initiator. The active energy ray-curable resin composition according to any one of claims 6 to 8, comprising a color pigment. The active energy ray-curable resin composition according to any one of claims 6 to 9, which is a molding material. The active energy ray-curable resin composition according to any one of claims 6 to 9, which is a film forming material. The active energy ray-curable resin composition according to any one of claims 6 to 11, which is a resist material composition. Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 6-12. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 11.