JP2010280812A - Reactive urethane compound, active energy ray-curable resin composition comprising the same and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material that permits photo-patterning, is heat-resistant, retains high insulating properties over a long period of time, has flexibility suitable for a flexible substrate and the like without detriment to fundamental properties of a solder resist, a color resist and the like and is hardly deteriorated or discolored even by high temperatures or light. <P>SOLUTION: A reactive polyurethane compound (A) is obtained by allowing an epoxy carboxylate compound (a), obtained by allowing an epoxy resin (i) containing no aromatic ring and bearing two epoxy groups in one molecule to react with a compound (ii) bearing both at least one polymerizable ethylenically unsaturated group and at least one carboxy group in one molecule, a compound (b) bearing both two hydroxy groups and at least one carboxy group in one molecule, and a compound (c) containing no aromatic ring and bearing two isocyanate groups in one molecule to react. An acid-modified product of the compound is provided. The active energy ray-curable resin composition comprises the compound. A cured product of the compound is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a reactive polyurethane compound that is hard to be modified or discolored by heat or light, can obtain a tough and flexible cured film, and is capable of photo-patterning by development, and an active energy ray curable type containing the same. The present invention relates to a resin composition, a cured product thereof, and further to its use.

  Printed circuit boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Accordingly, there is a need for so-called solder resists for film forming materials that cover circuits. It is getting higher and higher. Specifically, with regard to heat resistance that can withstand the heat generation of elements during board manufacturing and operation using solder, etc., reliability by maintaining long-term high insulation, performance that can withstand chemical treatment such as plating, etc. Although there is a demand for a film-forming material having a tougher cured product performance, a material satisfying these characteristics has not been found.

  Further, in recent years, the use of flexible printed wiring boards such as flexible boards has been expanded. In the case of a flexible substrate, a circuit protection is generally performed by laminating a so-called cover lay film. However, there is a problem in productivity because it takes time and effort. On the other hand, attempts have been made to use a developable solder resist type film forming material, but the film is rigid and can follow bending, and at the same time, other required materials. No material has been found that meets the properties.

  In addition, a wide range of attempts have been made to use light-emitting diodes, so-called LEDs, as a light source. For printed wiring boards on which LED elements are mounted, a white film is formed on the mounting board in order to extract light more effectively. The use of materials is common. Although this film-forming material, that is, a solder resist, satisfies the various characteristics required for the above-mentioned solder resist, a material that does not change in coloring or the like during an element mounting process or a long period of use is desired. No material has yet been found.

  In addition, color resists used in manufacturing color filters used in so-called liquid crystal displays and organic EL displays are also modified and discolored by heat treatment during production, heat during use, and light, as with printed wiring boards. Therefore, there is a problem that the color reproducibility deteriorates. Therefore, there is a demand for a resist binder that can be finely patterned by alkali development and has no discoloration. Further, regarding the color filter, since a flexible color filter is required to realize a flexible display, the same flexibility as a flexible substrate is required.

  However, when epoxy acrylate having an aromatic ring used in conventional solder resists and color resists is used, heat treatment such as soldering at the time of element mounting, heat from LED elements or backlight when used as an actual substrate, Under the influence of light, the resist resin itself deteriorates and discolors, and there remains a problem in practical use.

  In order to solve the above-mentioned various problems, Patent Documents 1 and 2 and the like describe attempts to use a compound having photoreactivity with an acrylic acid copolymer as a composition, and imparting reactivity to the acrylic acid copolymer. For this reason, attempts have been made to graft polymerizable ethylenically unsaturated groups. However, with these materials, it is difficult to obtain sufficient sensitivity for photo-patterning, and since it does not have sufficient heat resistance, heat resistance such as heat treatment such as soldering at the time of element mounting and insulation for a long period of time are not possible. The reliability to keep was not enough.

  In addition, an attempt has been reported to use an epoxy resin having an alicyclic structure to derive a reactive epoxycarboxylate compound and use it as a white solder resist (see Patent Document 3). However, this material lacks flexibility and is difficult to use on a flexible substrate.

  Patent Documents 4 and 5 and the like include a difunctional epoxycarboxylate compound containing an aromatic ring, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, and a reactive urethane acrylate compound comprising a diisocyanate compound. Attempts to use it in resists are described. However, there is no description about the use of a reactive urethane compound derived from an epoxy resin containing no aromatic ring for a solder resist or the like.

JP 2007-322546 A JP 2008-134621 A JP 2008-211036 A JP 09-52925 A Japanese Patent Laid-Open No. 2001-33960

  In view of the above, the present invention is capable of photo-patterning, has heat resistance that can withstand the heat generation of the element at the time of manufacturing or operating a substrate using solder, etc., reliability by maintaining high insulation for a long time, plating, etc. Material that can be used for solder resists that are resistant to chemical processing, and has the flexibility that can be used for flexible substrates without impairing the basic characteristics of color resists, etc. We intend to provide materials that have the ability to resist discoloration.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained an epoxy carboxylate compound obtained from an epoxy resin containing no aromatic ring, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule. The present inventors have found a reactive polyurethane compound obtained from a compound having two isocyanate groups in one molecule, an acid-modified compound thereof, an active energy ray-curable resin composition containing the compound, and a cured product thereof.

  That is, the present invention includes an epoxy resin (i) having no aromatic ring and having two epoxy groups in one molecule, one or more polymerizable ethylenically unsaturated groups and one or more ones in one molecule. An epoxycarboxylate compound (a) obtained by reacting with a compound (ii) having a carboxyl group, a compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, and no aromatic ring, The present invention also relates to a reactive polyurethane compound (A) obtained by reacting a compound (c) having two isocyanate groups in one molecule.

Further, the present invention relates to an acid-modified reactive polyurethane compound (B) obtained by reacting the reactive polyurethane compound (A) with a polybasic acid anhydride (d).
Furthermore, the present invention relates to an active energy ray-curable resin composition containing the reactive polyurethane compound (A) and / or the acid-modified reactive polyurethane compound (B).
Furthermore, it is related with the said active energy ray hardening-type resin composition containing reactive compounds (C) other than a compound (A) and a compound (B).
Furthermore, it is related with the said active energy ray hardening-type resin composition containing a color pigment.

Furthermore, it is related with the said active energy ray hardening-type resin composition which is a transparent material for shaping | molding.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a coloring film formation material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a material for light permeable film formation.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a resist material.

Furthermore, it is related with the hardened | cured material of the said active energy ray curable resin composition.
Further, the present invention relates to an article overcoated with a cured product of the active energy ray-curable resin composition.

  The reactive polyurethane compound of the present invention, the acid-modified compound thereof, the active energy ray-curable resin composition containing the same, and the cured product thereof can be photo-patterned, and can be used at the time of manufacturing or operating a substrate using solder or the like. Heat resistance that can withstand the heat generation of the element, reliability by maintaining high insulation for a long time, materials that can be used for solder resists that are resistant to chemical treatments such as plating, and basic characteristics such as color resists are not impaired It is a material that has flexibility that can be used for a flexible substrate and the like, and further has a property of being hardly denatured or discolored by high temperature or light.

  As a result, it is possible to provide a white solder resist or the like that is not colored even after long-term use. For example, it can be suitably used for a solder resist such as an LED mounting substrate used as a light source. Moreover, it is suitable as a resist binder for color filters such as a liquid crystal display and an organic EL display and an optical waveguide forming material by taking advantage of the feature that is difficult to color. Furthermore, since it also has a softness | flexibility, when it uses for a flexible substrate, the effect of this invention can be exhibited to the maximum.

  The reactive polyurethane compound (A) of the present invention comprises an epoxy resin (i) that does not contain an aromatic ring and has two epoxy groups in one molecule, and one or more polymerizable ethylenic polymers in one molecule. An epoxycarboxylate compound (a) obtained by reacting a compound having a saturated group and one or more carboxyl groups (ii), a compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule; It can be obtained by reacting a compound (c) that does not contain an aromatic ring and has two isocyanate groups in one molecule. That is, the reactive polyurethane compound (A) of the present invention comprises an epoxy carboxylate-forming step for obtaining an epoxy carboxylate compound (a) by reacting an epoxy resin (i) with a compound (ii), and the epoxy carboxylate compound. (A) reacting a compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a compound (c) not containing an aromatic ring and having two isocyanate groups in one molecule It can be obtained with two reaction steps of the urethanization step.

  The epoxycarboxylate compound (a) obtained in the epoxycarboxylation step is obtained by reacting the epoxy resin (i) with the compound (ii) to form two ethylenically unsaturated groups polymerizable in one molecule and epoxy. It has two hydroxyl groups derived from the resin (i).

  In the subsequent urethanization step, the hydroxyl group of the epoxy carboxylate compound (a) and the compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule is urethanized with the compound (c) having an isocyanate group. Thus, the reactive polyurethane compound (A) is obtained.

  The epoxy resin (i) which does not contain an aromatic ring and has two epoxy groups in one molecule used in the epoxy carboxylation step is a characteristic component of the present invention. Since it does not contain an aromatic ring, it becomes possible to suppress denaturation and discoloration with respect to heat and light, and since it has two epoxy groups, it can be urethanized using a hydroxyl group produced after epoxy carboxylation. At this time, the molecular weight of the resulting reactive polyurethane compound (A) cannot be adjusted with a monofunctional epoxy compound, and a tri- or higher functional epoxy compound has a multi-branched structure to obtain a suitable cured product property. Is difficult.

The epoxy resin (i) is preferably a compound represented by the general formula (I).
[Chemical 1]
X-R-X (I)
(In the formula, X represents a functional group having an epoxy group, and R represents an organic residue containing no direct bond or aromatic ring.)

  Examples of the functional group having an epoxy group in the general formula (I) include an aliphatic substituent having an epoxy group such as a glycidyl ether group and a glycidyl ester group, a 3,4-epoxycyclohexyl ether group, and a 3,4-epoxycyclohexane. Examples include alicyclic substituents having an epoxy group such as a carboxylyl ester group.

The organic residue containing no aromatic ring in the general formula (I) is not particularly limited as long as it does not contain an aromatic ring.
When the compound represented by the general formula (I) is a compound obtained by reacting, for example, a diol compound or a dicarboxylic acid compound with epichlorohydrin, glycidol, cyclohexenecarboxylic acid, cyclohexenemethanol or the like, R is It becomes a residue of the diol compound, dicarboxylic acid compound and the like.

  Examples of the organic residue not containing an aromatic ring include a linear hydrocarbon residue, a cyclic hydrocarbon residue, a polyalkylene glycol residue, a polyester diol residue, and a cyclic ether diol residue.

  Examples of linear hydrocarbon residues include ethylene glycol residues, propylene glycol residues, butylene glycol residues, pentanediol residues, hexanediol residues, heptanediol residues, octanediol residues, and nonanediol. A residue, a decanediol residue, an adipic acid residue, a sebacic acid residue, etc. are mentioned, Preferably it is C2-C30, More preferably, an organic residue of 6-18 is preferable. When the number of carbon atoms is less than this range, the obtained cured product is insufficient in flexibility, and when it is large, the toughness is insufficient.

  Examples of the cyclic hydrocarbon residue include cyclohexanediol residue, cyclohexanedimethanol residue, isobornyldiol residue, norbornenediol residue, tricyclodecanediol residue, hydrogenated bisphenol A residue, and hydrogenated bisphenol. F residues, hydrogenated biphenol residues and the like can be mentioned, and preferably an organic residue having 2 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. When the number of carbon atoms is less than this range, the obtained cured product is insufficient in flexibility, and when it is large, the toughness is insufficient. The substitution position of the substituent is not particularly limited as long as substitution is possible.

  Examples of the polyalkylene glycol residue include a polyethylene glycol residue, a polypropylene glycol residue, a polybutylene glycol residue, and the like. The number average molecular weight of the polyalkylene glycol is preferably about 62 to 5000, and about 500 to 2000. More preferred. When the number average molecular weight is smaller than this range, the obtained cured product has insufficient flexibility, and when it is larger, the toughness is insufficient.

  Examples of the polyester diol residue include a polycaprolactone diol residue, an ethylene glycol adipate diol residue, a linear hydrocarbon polycarbonate diol residue, a cyclic hydrocarbon polycarbonate diol residue, and the like. The average molecular weight is preferably about 100 to 5,000, more preferably about 500 to 2,000. When the number average molecular weight is smaller than this range, the obtained cured product has insufficient flexibility, and when it is larger, the toughness is insufficient.

  Examples of the cyclic ether diol residue include a spiro glycol residue having a spiro ring structure, a dioxane glycol residue having an acetal ring structure, and the like.

  Among these, a compound having a cyclic structure such as a cyclohexane ring structure, a spiro ring structure, or an acetal ring structure in the molecule is preferable in view of the heat resistance of the cured product. That is, a compound in which the organic residue R has the alicyclic structure or the functional group X having an epoxy group contains an alicyclic epoxy group is preferable.

  Further, when an aliphatic alcohol is glycidyl etherified with epichlorohydrin to obtain an epoxy resin (i), chlorine derived from epichlorohydrin tends to remain. When used in solder resists and the like that require long-term insulation, this chlorine causes circuit wiring breaks and short circuits due to ion migration. Therefore, purification is performed by molecular distillation or the like, an epoxy resin produced without using epichlorohydrin is used, or an aromatic ring is selectively hydrogenated after glycidyl etherification of an aromatic phenol with epichlorohydrin. It is preferable to use a nuclear hydrogenated epoxy resin.

  A preferable range of chlorine contained is 0 to 0.2% by weight, more preferably 0 to 0.2% by weight of the total chlorine contained in the epoxy resin (i) (according to a measurement method based on JIS K7243-3: 2005). 1% by weight.

  The case where R is directly bonded includes, for example, 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Celoxide 2021).

The compound (ii) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule used in the epoxy carboxylation step is obtained by reacting the epoxy resin (i) with an epoxy carboxylate reaction. While leading to a diol compound, it plays a role of introducing an ethylenically unsaturated group into the reactive polyurethane compound (A).
The compound (ii) is preferably a compound having no hydroxyl group, for example, (meth) acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated group-containing compound. Examples include a reaction product with a glycidyl compound.

Examples of (meth) acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, and (meth) acrylic acid and ε-caprolactone reaction. Products, saturated or unsaturated dibasic acid anhydrides, (meth) acrylate derivatives having one hydroxyl group in one molecule, half-esters that are equimolar reactants, saturated or unsaturated dibasic acids and monoglycidyl ( And half-esters which are equimolar reactants with meth) acrylate derivatives.
Among these, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is preferable in terms of sensitivity when an active energy ray-curable resin composition is used.

  In the epoxy carboxylation step, it is preferable to use 90 to 120 equivalent% of the compound (ii) with respect to 1 equivalent of the epoxy group of the epoxy resin (i). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of compound (ii) charged is larger than this, excess carboxylic acid remains, which is not preferable. On the other hand, if the amount is too small, unreacted epoxy groups remain, which causes a problem in the stability of the produced resin.

  In the epoxycarboxylation step, the reaction may be performed without solvent or diluted with a solvent. The solvent is not particularly limited as long as it is an inert solvent for the epoxycarboxylation reaction, and an inert solvent is also used in the subsequent urethanization step and the acid addition step described below as necessary. It is preferable. The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, and is preferably about 30 to 100% by weight, more preferably 50 to 90% by weight as the solid content.

  Examples of the solvent include hydrocarbon solvents such as aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures thereof. Examples include petroleum ether, white gasoline, and solvent naphtha.

  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 monoacetate, diethylene glycol monomethyl ether monoacetate, and diethylene glycol monoethyl ether monoester. Mono, such as acetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, succinate Polycarboxylic acid such as dialkyl acid and dialkyl adipate Alkyl esters, and the like.

  Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, 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. And glycol ethers such as tetrahydrofuran, and cyclic ethers such as tetrahydrofuran.

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

  In addition, the reactive compound (C) described later may be used alone or as a mixed organic solvent. In this case, the active energy ray-curable resin composition can be used as it is.

  In the epoxy carboxylation step, it is preferable to use a catalyst in order to promote the reaction. The amount of the catalyst used is a reaction product, that is, the above-mentioned epoxy resin (i), compound (ii), and in some cases, a solvent, etc. Is about 0.1 to 10% by weight with respect to the total amount of the reaction product added. The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

  Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and zirconium octoate. A basic catalyst etc. are mentioned.

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

  In the epoxycarboxylate conversion step, the end point is when the acid value of the sample becomes 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling appropriately.

The compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule used in the urethanization step introduces a carboxyl group into the reactive polyurethane compound (A), and an alkaline aqueous solution can be used during photopatterning. It is for melting.
Examples of the compound (b) include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid and the like. Of these, dimethylolpropionic acid and dimethylolbutanoic acid are preferred in view of the availability of raw materials.

The compound (c) not containing an aromatic ring used in the urethanization step and having two isocyanate groups in one molecule is composed of an epoxy carboxylate compound (a) and two hydroxyl groups and one or more in one molecule. A reactive polyurethane compound (A) is produced by a urethanation reaction with the hydroxyl group of the compound (b) having a carboxyl group. As a result, a material having suitable flexibility can be obtained. Moreover, the denaturation and discoloration by heat and light can be suppressed by not containing an aromatic ring.
Examples of the compound (c) include linear diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, aliphatic cyclic diisocyanates such as isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated methylene bisphenylene diisocyanate. Is mentioned.

  In the urethanization step, the compound (c) having an isocyanate group is preferably mixed with the mixture of the epoxycarboxylate compound (a) and the compound (b).

  When producing the reactive polyurethane compound (A) of the present invention, (number of moles of epoxy carboxylate compound (a) + number of moles of compound (b)) / value of the number of moles of compound (c) having an isocyanate group, That is, the ratio of the hydroxyl group to the isocyanate group in the reaction system is preferably in the range of 1.05 to 2, particularly preferably in the range of 1.1 to 1.5. This is to improve the storage stability of the reactive polyurethane compound (A) by preventing the isocyanate group from finally remaining in the urethanization reaction. When the ratio of hydroxyl groups to isocyanate groups in the reaction system is larger than this value, the molecular weight of the resulting reactive polyurethane compound (A) becomes too small to make it difficult to obtain a tough cured product. In addition, there is an adverse effect that the molecular weight of the obtained resin becomes too large and developability is poor.

  Furthermore, when manufacturing a reactive polyurethane compound (A), the value of the number-of-moles of an epoxy carboxylate compound (a) / the number-of-moles of a compound (b) is preferable in the range of 0.1-4, 0.3-2 The range of is particularly preferable. When this value is larger than 4, the amount of carboxyl groups in the reactive polyurethane resin (A) decreases and it is difficult to impart the required developability. Moreover, when this value is smaller than 0.1, the reactive group in the reactive polyurethane resin (A) decreases, and it is difficult to impart sensitivity and toughness of the coating film.

In the urethanization step, the reaction may be performed without a solvent or may be diluted with a solvent. The solvent is not particularly limited as long as it is an inert solvent for the urethanization reaction. The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, but is preferably about 30 to 99% by weight, more preferably 50 to 90% by weight as the solid content. Moreover, when it manufactures using a solvent in the epoxy carboxylate conversion process which is a previous process, if it is inert to both reaction, it can also use for the urethanization process which is a next process directly, without removing a solvent.
As this solvent, the solvent illustrated in the said epoxy carboxylate-ized process is mentioned. In addition, as described above, the reactive compound (C) described later may be used alone or as a mixed organic solvent, and in this case, it can be used as it is as an active energy ray-curable resin composition.

  As the thermal polymerization inhibitor and the like, the same compounds as in the epoxy carboxylation step can be used.

In the urethanization step, the reaction can be carried out substantially without catalyst, but a catalyst can also be used to accelerate the reaction. When the catalyst is used, the amount used is based on the total amount of the reaction product, that is, the carboxylate compound (a), the compound (b), the compound (c) having an isocyanate group, and optionally the reaction product to which a solvent is added. About 0.01 to 1% by weight. The reaction temperature is 40 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
The catalyst is preferably a known basic catalyst such as a Lewis base catalyst such as tin ethylhexanoate or tin octoate.

In the urethanization step, the reaction end point is set at a time when almost no isocyanate groups remain. This reaction end point may be determined by observing a peak around 2250 cm ⁻¹ derived from an isocyanate group by infrared absorption spectrum measurement, or using a titration method according to JIS K1556: 1968 or the like.

The molecular weight range of the reactive carboxylate compound (A) of the present invention thus obtained is preferably in the range of 1,000 to 30,000 in terms of polystyrene weight average molecular weight in GPC (gel permeation chromatography), more preferably 1 , 500 to 20,000.
When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited. When the molecular weight is larger than this, the viscosity becomes high and coating or the like becomes difficult.

  When the reactive polyurethane compound (A) of the present invention is used as an alkali development type resist, the solid content acid value of the finally obtained reactive polyurethane compound (A) (according to JIS K5601-2-1: 1999). ) Is preferably 30 to 120 mg · KOH / g, more preferably 40 to 105 mg · KOH / g. When the solid content acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good developability with an alkaline aqueous solution. That is, a good patterning property and a management range for overdevelopment are widened.

  The present invention also includes an acid-modified reactive polyurethane compound (B) obtained by reacting a reactive polyurethane compound (A) with a polybasic acid anhydride (d). By doing so, the acid value required for alkali development can be further added depending not only on the compound (b) but also on the required properties of the resin. In the present invention, this reaction step is referred to as an acid addition step.

  The acid addition step is a step in which a polybasic acid anhydride (d) is reacted with a hydroxyl group remaining in the reactive polyurethane compound (A) to introduce a carboxyl group via an ester bond. Accordingly, it is impossible to add an acid beyond the equivalent of the hydroxyl group remaining after the urethanization step.

  As the polybasic acid anhydride (d), any compound having an acid anhydride structure in one molecule can be used, but a compound excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance and the like can be used. From the point of giving, for example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride Or maleic anhydride etc. are mentioned.

  The acid addition step is performed by adding the polybasic acid anhydride (d) to the reactive polyurethane compound (A). The amount of the polybasic acid anhydride (d) used depends on the set value of the reactive polyurethane compound (A), that is, the acid value derived from the compound (b), the amount of residual hydroxyl groups, and the required acid value. It can be changed as appropriate.

  However, when the acid-modified reactive polyurethane compound (B) of the present invention is used as an alkali development type resist, the solid content acid value (based on JIS K5601-2-1: 1999) is 30 to 120 mg · KOH / g, More preferably, a calculation amount of 40 to 105 mg · KOH / g is charged. When the solid content acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good developability with an alkaline aqueous solution. That is, a good patterning property and a management range for overdevelopment are widened.

  In the acid addition step, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the amount of the reactants, that is, the reactive polyurethane compound (A), the polybasic acid anhydride (d) and optionally the solvent. It is about 0.1 to 10 weight% with respect to the total amount of the reaction material which added etc. The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

  Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. Can be mentioned.

In the acid addition step, the reaction may be performed without solvent or diluted with a solvent. The solvent is not particularly limited as long as it is an inert solvent for the acid addition reaction. Moreover, when it manufactures using a solvent in the urethanization process which is a previous process, if it is inert to both reaction, it can also use for the acid addition process which is a next process directly, without removing a solvent.
The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, but is preferably about 30 to 90% by weight, more preferably 50 to 80% by weight as the solid content.

  As this solvent, the solvent similar to the said epoxy carboxylate-ized process or a urethanation process can be used, for example. In addition, the reactive compound (C) described below may be used alone or as a mixed organic solvent, and in this case, it can be used as it is as an active energy ray-curable resin composition.

  As the thermal polymerization inhibitor and the like, the same compounds as in the epoxy carboxylate-forming step and urethanization step can be used.

  In the acid addition step, the acid value of the reaction product is measured by the above-mentioned method while appropriately sampling, and the end point is determined when the measured acid value falls within the range of plus or minus 10% of the set acid value.

  Examples of the reactive compound (C) other than the compound (A) and the compound (B) that may be contained in the active energy ray-curable resin composition of the present invention include, for example, radical-reactive (meth) acrylates, cations Examples thereof include so-called reactive oligomers such as reactive epoxy compounds and vinyl compounds sensitive to both.

  Examples of the radical reaction type acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, urethane (meth) acrylate, polyester (meth) acrylate, and other epoxy (meth) acrylates.

  Monofunctional (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl Examples include ether, phenethyl (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 glycol 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 , Hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, neopentyl glycol hydroxybivalate Di (meth) acrylate of ε-caprolactone adduct, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane Tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or its ethylene oxide adduct, etc. Can be mentioned.

  Furthermore, a urethane (meth) acrylate having a functional group that reacts with active energy rays and a urethane bond in the same molecule, a polyester (meth) acrylate having a functional group that reacts with active energy rays and an ester bond in the same molecule, other Compound (A) derived from an epoxy resin and having functional groups that react with active energy rays in the same molecule, epoxy (meth) acrylate other than compound (B), and reactivity in which these bonds exist in a complex manner An oligomer etc. are mentioned.

  The cationic reaction type epoxy compounds are not particularly limited as long as they are compounds 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 (Union Carbide, Cyracure UVR-6110, etc.), 3,4-epoxycyclohexylethyl 3 ′, 4′-epoxycyclohexanecarboxylate, vinyl Cyclohexene dioxide (manufactured by Union Carbide, ELR-4206, etc.), limonene dioxide (manufactured by Daicel Chemical Industries, Celoxide 3000, etc.), allylcyclohexene dioxide, 3 , 4-Epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxy (Cyclohexyl) adipate (manufactured by Union Carbide, Cyracure UVR-6128, etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) Examples include ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

  Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like.
Examples of styrenes include styrene, methyl styrene, and ethyl styrene.
Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Among these, as the reactive compound (C), radical reaction type (meth) acrylates are particularly preferable. When using a cation-reactive compound, it is necessary to use a two-component mixed-use type so that the carboxylic acid and the epoxy group do not react.

  The reactive polyurethane compound (A) and / or acid-modified reactive polyurethane compound (B) of the present invention is mixed with the reactive compound (C) other than the compound (A) and the compound (B) as necessary. The active energy ray-curable resin composition of the present invention can be obtained. At this time, you may add another component suitably according to a use.

  In the active energy ray-curable resin composition of the present invention, the reactive polyurethane compound (A) and / or the acid-modified reactive polyurethane compound (B) in the composition is preferably 5 to 97% by weight, particularly preferably 10%. The reactive compound (C) other than ˜87 wt%, compound (A) and compound (B) is preferably contained in an amount of 3 to 95 wt%, particularly preferably 3 to 90 wt%. If necessary, other components may be included up to about 70% by weight.

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

The color pigment that may be contained in the active energy ray-curable resin composition of the present invention is used to make the active energy ray-curable resin composition a colored material. Since the present invention is a material that is less colored even by exposure to heat or light, it is suitable for use in applications using colored materials.
Examples of the coloring pigment include organic pigments such as phthalocyanine, azo, and quinacridone, and inorganic pigments such as carbon black and titanium oxide. Of these, the use of a material colored in a color that is sensitive to a change in color tone due to yellow discoloration such as white, green, and blue is particularly preferable.

  In the present invention, the molding material refers to an uncured composition placed in a mold or pressed against a mold to form an object and then cured by active energy rays, or the uncured composition is focused light such as a laser. Refers to a material used for the purpose of irradiating, curing and molding. That is, a sheet formed in 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 finely processed into an uncured composition, and more particularly thermal Applications such as peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have severe optical requirements, can be mentioned.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Ink materials such as gravure ink, flexo ink, silk screen ink, offset ink, coating materials such as hard coat, top coat, overprint varnish, clear coat, various adhesives and adhesives for laminating, optical disc, etc. Uses such as adhesive materials, solder resists, etching resists, resist materials such as resists for micromachines, and the like. Further, a so-called dry film in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to the originally intended substrate to form a film corresponds to the film-forming material.

  Of these, the reactive polyurethane compound (A) and / or the acid-modified reactive urethane compound (B) is preferably used as an alkaline water developing resist material composition taking advantage of the feature of being soluble in an alkaline aqueous solution.

  In the present invention, the resist material means that a film layer of the composition is formed on a substrate, and then an active energy ray such as ultraviolet rays is partially irradiated, and the physical difference between an irradiated part and an unirradiated part is determined. An active energy ray-sensitive material to be used for drawing. It is a material used for the purpose of removing the irradiated part or the unirradiated part by some method, for example, dissolving it with a solvent or an alkaline solution, and performing drawing.

  The active energy ray-curable resin composition, which is a resist material of the present invention, can be used for various materials that can be patterned. For example, it is particularly useful for solder resist materials and interlayer insulation materials for build-up methods. Furthermore, it can be used as an optical waveguide for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates, and the like.

  Especially suitable applications are permanent resist applications such as solder resists that have the purpose of coloring, taking advantage of the characteristics of being able to obtain a cured product that is flexible but strong, and that is not easily altered or discolored by heat or light, Use of a color resist such as a color filter is preferred.

  Furthermore, when used for flexible substrate applications that require flexibility, the effects of the present invention can be maximized.

  The method for forming a film using the active energy ray-curable resin composition of the present invention is not particularly limited, and includes intaglio printing methods such as gravure, relief printing methods such as flexo, stencil printing methods such as silk screens, and offsets. Various coating methods such as a lithographic printing method, a roll coater, a knife coater, a die coater, a curtain coater, and a spin coater can be arbitrarily employed.

  A cured product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with an active energy ray is also included in the present invention.

  Furthermore, the active energy ray-curable resin composition of the present invention may contain other components up to 70% by weight in the resin composition in accordance with various uses. Examples of other components include a photopolymerization initiator, various additives, pigment materials, a volatile solvent for adjusting viscosity for imparting coating suitability, and the like.

  As the photopolymerization initiator, a radical photopolymerization initiator, a cationic photopolymerization initiator, or the like can be used.

  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-methylphenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Acetophenones such as phenyl] -2-morpholinopropan-1-one; anthra such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Nons; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone and 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc. These radical-type photoreaction initiators.

  Examples of the cationic photopolymerization initiator include Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, and others. And a photoacid generator.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L). Etc.).
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 (manufactured by Union Carbide, Cyracure UVI-6990, etc.), triphenylsulfonium hexafluoroantimonate (manufactured by Union Carbide, Cyracure UVI-6974, etc.), and the like. Can be mentioned.
Examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate.

Examples of other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (manufactured by AKZO, Trigonal PI, etc.), 2,2-dichloro-1- [4, and the like. -(Phenoxyphenyl)] ethanone (manufactured by Sandoz, Sandray 1000, etc.), α, α, α-tribromomethylphenylsulfone (manufactured by Iron Chemical Co., Ltd., BMPS, etc.) and the like.
Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) triazine, 2-trichloromethyl-4- (4′-methoxyphenyl) -6-triazine (manufactured by Panchi, Triazine A and the like), 2-trichloromethyl-4- (4′-methoxystyryl) -6-triazine (manufactured by Panchim, Triazine PMS, etc.), 2-trichloromethyl-4-pipronyl-6-triazine (manufactured by Panchim, Triazine PP, etc.), 2-trichloromethyl-4- (4′-methoxynaphthyl) -6-triazine (manufactured by Panchim, Triazine B, etc.), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloro Methyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2- (2′-furylethyl) Emissions) -4,6-bis (manufactured by trichloromethyl) -s-triazine (Sanwa Chemical Co., Ltd.).
Examples of the baud rate initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye.

  Examples of other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (black). Biimidazole manufactured by Kasei Chemical Co., Ltd.), 2,2-azobis (2-aminopropane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazolin-2-yl) propane] Dihydrochloride (Wako Pure Chemical Industries, VA044, etc.), [Eta-5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, eta)-(methylethyl) benzene] iron (II) hexafluorophosphonate (manufactured by Ciba Geigy, Irgacure 261, etc.), bis (y5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) ) Phenyl] titanium (Ciba Geigy, CGI-784, etc.).

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 photopolymerization initiators may be used in combination.
These photopolymerization initiators may be used alone or in combination of two or more as appropriate.

  Examples of the various additives include thermosetting catalysts such as melamine, thixotropy imparting agents such as aerosil, silicone and fluorine leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, An antioxidant etc. are mentioned.

  Examples of the pigment material include extender pigments not intended to be colored, such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

  Resins that are not reactive with 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 or synthetic rubbers, acrylic resins, polyolefin resins, or modified products thereof can also be used. These are preferably used in the resin composition in the range of up to 40% by weight.

  In particular, when a resin composition containing an acid-modified reactive polyurethane compound (B) is used for solder resist applications, it is preferable to use a known general epoxy resin as a resin having no reactivity with active energy rays. An epoxy resin which has a carboxyl group derived from the compound (B) even after being cured by active energy rays and the cured product tends to be inferior in water resistance and hydrolyzability, but has no reactivity to active energy rays. Thus, the remaining carboxyl group can be further reacted to form a strong crosslinked structure, thereby enhancing the performance.

  The viscosity adjusting volatile solvent may be added to the resin composition in a range of 50 wt%, more preferably up to 35 wt%.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.
The softening point and epoxy equivalent were measured under the following conditions.
(1) Epoxy equivalent: measured by a method according to JIS K7236: 2001 (2) Total chlorine: measured by a method according to JIS K7243-3: 2005 (3) Acid value: measured by a method according to JIS K0070: 1992 (4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, temperature 40 ° C.
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1 Synthesis of Epoxy Carboxylate Compound (a) (Epoxy Carboxylation Step)
Epoxy resin (i) shown in Table 1 below is 1 mol of epoxy group (the same g number as epoxy equivalent (WPE; g / eq)), and 1 mol of acrylic acid (abbreviation AA, molecular weight 72) as compound (ii). (72 g), 3 g of triphenylphosphine as a catalyst, propylene glycol monomethyl ether monoacetate (abbreviation PGMAc) as a solvent was added so that the solid content would be 80%, and the mixture was reacted at 100 ° C. for 24 hours to obtain an epoxycarboxylate compound (a ) A solution was obtained. The reaction end point was determined by solid content acid value (AV; mgKOH / g). The solid content acid value was converted from the solution acid value measured in the reaction system.

Synthesis Example 2 Synthesis of Epoxy Carboxylate Compound Having Aromatic Ring The reaction was performed in the same manner as in Synthesis Example 1 except that the amount of bisphenol A type epoxy resin described in Table 1 was used as the epoxy resin.

Table 1

Abbreviation WPE described in Table 1: Epoxy equivalent (g / eq)
TCl: Total chlorine (%)
AV: Solution acid value in the reaction system; mgKOH / g
X: Type of epoxy group in general formula (I) and bonding form thereof GEth: Glycidyl ether group CEst: 3,4-epoxycyclohexanecarboxyl ester group CEth: 3,4-epoxycyclohexyl ether group R: General formula (I) Diol residue in HD: hexanediol residue (linear hydrocarbon residue)
PTMG650: polytetramethylene glycol residue (polyalkylene glycol residue; average molecular weight 650)
PCDL800: Polycarbonate diol residue (polyester diol residue; average molecular weight 800)
CHDM: Cyclohexanedimethanol residue (cyclic hydrocarbon residue)
H-BisA: hydrogenated bisphenol A residue (cyclic hydrocarbon residue)
TCD: Tricyclodecane dimethanol residue (cyclic hydrocarbon residue)
DOG: Dioxane glycol residue (cyclic ether diol residue)
None: No linking group (direct bond)
Bis-A: Bisphenol A residue (bisphenol A residue having an aromatic ring)

Example 1: Production of reactive polyurethane compound (A) (urethanization step)
The amount of the epoxycarboxylate compound (a) solution synthesized in Synthesis Example 1 in the reaction tank described in Table 2 (in terms of solid content), a compound having both two hydroxyl groups and one or more carboxyl groups in one molecule (b ) Dimethylolpropionic acid in the amount shown in Table 2, propylene glycol monomethyl ether acetate (abbreviated as PGMAc) as a solvent, and 50% of the reactive polyurethane compound (A) as a solid content were added and dissolved with stirring. Further, 1 g of tin octoate was added as a catalyst and heated to 100 ° C. Subsequently, as a compound (c) which does not contain an aromatic ring and has two isocyanate groups in one molecule, the diisocyanate described in Table 2 was added and reacted using a dropping funnel. Reaction was continued for 2 hours after completion | finish of dripping, and it confirmed that there was no absorption peak derived from an isocyanate group in an infrared absorption spectrum, and obtained the reactive polyurethane compound (A).

Comparative Example 1 Production of Reactive Polyurethane Compound Having Aromatic Ring Comparative Example 1-1 uses the epoxy carboxylate compound synthesized in Synthesis Example 2, and uses the reactive polyurethane compound having an aromatic ring in the same manner as in Example 1. Manufactured. In Comparative Example 1-2, a reactive polyurethane compound having an aromatic ring was produced in the same manner as in Example 1 using a compound having two isocyanate groups having an aromatic ring.

Table 2

Abbreviations DMPA: dimethylolpropionic acid HMDI: hexamethylene diisocyanate TMDI: trimethylhexamethylene diisocyanate IPDI: isophorone diisocyanate TDI: tolylene diisocyanate (aromatic)
(A + b) / c: (number of moles of compound (a) + number of moles of compound (b)) / value of number of moles of compound (c) a / b: number of moles of compound (a) / of compound (b) Mole value AV: Acid value at the end of the reaction (solid content conversion value); mgKOH / g

Example 2: Production of acid-modified reactive polyurethane compound (B) (acid addition step)
To the reaction vessel, the amount of the reactive polyurethane compound (A) produced in Example 1 was added in the amount shown in Table 3 (in terms of solid content), the acid anhydride shown in Table 3 was added, and propylene glycol monomethyl ether acetate as the solvent. (Abbreviation PGMAc) was added to the acid-modified reactive polyurethane compound (B) to a solid content of 50% and dissolved by stirring. The solution was heated at 80 ° C. for 10 hours, the acid value was measured, and the completion of the reaction was confirmed.

Comparative Example 2: Production of an acid-modified reactive urethane compound having an aromatic ring (acid addition step)
Using the reactive polyurethane compound produced in Comparative Example 1 in the reaction vessel, an acid-modified reactive urethane compound having an aromatic ring was produced in the same manner as in Example 2.

Table 3

Abbreviations THPA listed in Table 3: Tetrahydrophthalic anhydride SA: Succinic anhydride AV (compound (A)): Acid value (converted to solid content) of raw material compound (A), mgKOH / g
AV (compound (B)): acid value of the produced compound (B) (in terms of solid content), mgKOH / g

Example 3: Preparation and evaluation of white solder resist composition for flexible substrate 54 g of reactive polyurethane compound (A) obtained in Example 1 or acid-modified reactive urethane compound (B) obtained in Example 2 and reaction HX-220 (trade name: manufactured by Nippon Kayaku Co., Ltd., diacrylate monomer) 3.5 g as a functional compound (C), 5 g of lucillin TPO (manufactured by BASF) as a photopolymerization initiator, and alicyclic as a curing component After blending 15 g of diepoxide resin (Celoxide 2021P: manufactured by Daicel Chemical Industries), 1 g of melamine as a thermosetting catalyst, 21 g of methyl ethyl ketone as a concentration adjusting solvent, and 30 g of titanium oxide (Typaque A-100: manufactured by Ishihara Sangyo) as a color pigment The resist resin composition was obtained by kneading with a three-mill and dispersing uniformly.
The obtained resist resin composition was applied to a copper laminated polyimide film using a silk screen method so that the film thickness after drying was approximately 20 microns. The coated substrate was heated in an electric oven at 80 ° C. for 60 minutes to dry the solvent.
Next, a Kodak step tablet No. for estimating the mask and sensitivity on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). 2 was irradiated with ultraviolet rays of 500 mJ / cm ² . Thereafter, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the non-irradiated part. It was washed with water and dried, and the printed circuit board was heated and cured in an electric oven at 150 ° C. for 60 minutes to obtain a cured film.

Sensitivity Evaluation Sensitivity was determined by the density portion of the step tablet remaining at the time of development in the exposed portion that passed through the step tablet. The greater the number of steps, the higher the sensitivity is determined (unit: step).

Evaluation of developability The developability was evaluated based on the so-called break time (unit: second) until the pattern-shaped portion was completely developed when the exposed portion that passed through the pattern mask was developed. It is preferable that development can be performed in a time of about 20 to 50 seconds. If it is shorter than this, the development is too early and a problem is likely to occur in the stability of the development. On the other hand, if it is too long, a problem of productivity arises.

Curability evaluation Curability evaluation was evaluated by pencil hardness of the cured film after heating at 150 ° C. The evaluation method was based on JIS K5600-5-4: 1999.

Evaluation of heat resistance Evaluation of heat resistance was performed by immersing in a 260 ° C. solder bath for 1 minute after flux treatment, taking out, washing with water and air-drying, and performing an adhesion test (JIS K5600-2-6: 1999).
○: No peeling △: Slight peeling ×: Peeling

Evaluation of coloring property The obtained substrate was exposed for 24 hours with a super UV tester (manufactured by Iwasaki Electric Co., Ltd.), and the coloring was visually evaluated.
○: Almost no color change △: Slightly discolored ×: Yellow discoloration is severe and practically unusable

Folding resistance evaluation A polyimide printed circuit board on which a cured resist film was formed was folded in a mountain with the cured film side up, and the bent portion was rubbed with fingers. The bent portion was returned to its original position, and the resist film was observed with an optical microscope. Samples that did not have any problem even when bent once were bent at the same place five times in total, and the resist film cracks in the bent portions were observed with an optical microscope.
◎: No crack even after repeated 5 times ○: No crack after bending once △: Slight cracking observed after one bending ×: Peeling

Table 4

As described above, from the evaluation results as a white solder resist, the reactive polyurethane compound containing an aromatic ring and the acid-modified reactive polyurethane compound containing an aromatic ring have been colored so strongly that they cannot be used substantially in the evaluation of colorability. It was. On the other hand, the reactive polyurethane compound (A) or acid-modified reactive polyurethane (B) of the present invention that does not contain an aromatic ring showed excellent performance in each test.
It is clear that the balance of developability and other characteristics can be adjusted by acid-modifying compound (A) to compound (B), and acid modification is a suitable means.
Example 4: Evaluation of long-term insulation of white solder resist composition

The solder resist composition produced in Example 3 is formed on a BT resin printed circuit board having a comb pattern of 100 μm in line and space so that the film thickness after drying by a silk screen method is about 20 μm. Coated. The substrate after coating was heated in an electric oven at 80 ° C. for 60 minutes for solvent drying. Subsequently, after irradiating 500 mJ / cm < ² > of ultraviolet rays with an ultraviolet exposure device, the printed circuit board was subjected to a heat curing reaction in an electric oven at 150 [deg.] C. for 60 minutes to obtain a cured film. A lead wire was connected to the obtained substrate, and the transition of the resistance value was observed under an environment with an environmental temperature of 85 ° C. and a relative humidity of 85% while applying a voltage of 100 volts. The time until the resistance value fell below 10 megohm was measured.
A: The resistance value was maintained for 2000 hours or more. A: The resistance value was maintained for 1000 hours or more. Δ: The resistance value was maintained for 500 hours or more. X: The resistance value was 10 mega ohms or less in less than 500 hours.

Table 5

Abbreviations in Table 5 TCl: Total chlorine (%)
AV: Solid content acid value of compound (A) or compound (B) (mgKOH / g)
R: Diol residue in general formula (I) HD: Hexanediol residue (linear hydrocarbon residue)
PTMG650: polytetramethylene glycol residue (polyalkylene glycol residue, average molecular weight 650)
CHDM: Cyclohexanedimethanol residue (cyclic hydrocarbon residue)
H-BisA: hydrogenated bisphenol A residue (cyclic hydrocarbon residue)
TCD: Tricyclodecane dimethanol residue (cyclic hydrocarbon residue)
None: No linking group (direct bond)

  From the above results, the example with a high total chlorine content (Example 4-4) shows a tendency that the long-term insulation performance is lowered as compared with the low chlorine example (Example 4-5) having the same skeleton. It was. It was also shown that those having an alicyclic skeleton in the skeleton have high insulating properties.

  As is apparent from the above test results, the reactive polyurethane compound (A) or the acid-modified reactive polyurethane compound (B) of the present invention has basic characteristics as a solder resist and is discolored. There are few, and it has high flexibility aptitude and long-term insulation characteristics.

  The active energy ray-curable resin composition of the present invention can be used as a hard coating material or a colored resist material that requires flexibility for alkali development, as a material having the characteristics of curability and flexibility, and further difficult to color. Are better. Examples of applications that can effectively exhibit this characteristic include, for example, active energy ray-curable printing inks, color resists, color resists and lens materials for LCDs that are particularly resistant to discoloration, that is, excellent color reproducibility over a long period of time, Furthermore, it can be particularly suitably used for flexible displays and the like.

Claims (11)

An epoxy resin (i) not containing an aromatic ring and having two epoxy groups in one molecule, and a compound having both one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule ( an epoxy carboxylate compound (a) obtained by reacting with ii), a compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, and no aromatic ring and in one molecule A reactive polyurethane compound (A) obtained by reacting a compound (c) having two isocyanate groups. An acid-modified reactive polyurethane compound (B) obtained by reacting the reactive polyurethane compound (A) according to claim 1 with a polybasic acid anhydride (d). An active energy ray-curable resin composition comprising a reactive polyurethane compound (A) and / or an acid-modified reactive polyurethane compound (B). Furthermore, active energy ray hardening-type resin composition of Claim 3 containing reactive compounds (C) other than a compound (A) and a compound (B). The active energy ray-curable resin composition according to claim 3 or 4, comprising a color pigment. The active energy ray-curable resin composition according to any one of claims 3 to 5, which is a light-transmitting molding material. The active energy ray-curable resin composition according to any one of claims 3 to 5, which is a colored film-forming material. The active energy ray-curable resin composition according to any one of claims 3 to 5, which is a light-transmitting film-forming material. The active energy ray-curable resin composition according to any one of claims 3 to 5, which is a resist material. Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 3-5. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 10.