JP5638866B2 - Polyurethane compound, active energy ray-curable resin composition containing the same, and use thereof - Google Patents

Description

In the present invention, the epoxy compound (i) having two epoxy groups in one molecule has at least one polymerizable ethylenically unsaturated group and one carboxyl group in a molecule represented by acrylic acid or the like. Unsaturated epoxycarboxylate compound (a) obtained by reacting compound (ii), compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, specific polyester diol compound (c), and A polyurethane compound (A) obtained by reacting a compound (d) having two isocyanate groups in one molecule, and an acid obtained by reacting the polyurethane compound (A) with a polybasic acid anhydride (e). The present invention relates to a modified polyurethane compound (B).
Since these all have a carboxyl group, they have photopatterning and developability with an alkaline aqueous solution, and have characteristics suitable as a resist material. And it is a material which can give the hardened | cured material which has high heat resistance, sclerosis | hardenability, outstanding softness | flexibility, bending resistance, insulation reliability etc. which maintain insulation for a long period of time in a high-dimensional balance.

  Furthermore, the present invention relates to an active energy ray-curable resin composition containing the polyurethane compound (A) and / or the acid-modified polyurethane compound (B), and a cured product thereof.

In recent years, with the miniaturization of electronic information equipment, the use of so-called flexible printed boards has increased due to the light, thin, and flexible characteristics of circuit boards.
Since the flexible printed circuit board is literally flexible, the material used for it has high photosensitivity, adhesion, scratch resistance, high mechanical, thermal, and electrical properties while having the characteristics of photo-patterning by alkali development. A strong film forming ability with high flexibility capable of following a flexible substrate while having necessary properties such as strength is required.

  In general, characteristics such as excellent sensitivity, curability, chemical resistance, and heat resistance are achieved by introducing more reactive groups into the main chain having a rigid skeleton and imparting a high crosslinking density. The Such resins have been suitably used in applications such as ordinary solder resists. However, this does not give the flexibility required for the flexible substrate.

On the other hand, in order to impart flexibility, it has been achieved by modestly introducing reactive groups into the flexible main chain, that is, by appropriately reducing the crosslinking density.
As described above, these properties are contradictory, and a solder resist material such as a flexible substrate is required to have a material that fuses these properties at a high level. Conventionally, however, epoxy acrylate materials are mainly used. I came. However, this material is excellent in properties such as chemical resistance and heat resistance, but has insufficient flexibility. Therefore, it is difficult to obtain a tough film having flexibility that can be applied to a flexible substrate, and a further film forming material has been desired.

  As an attempt to solve these problems, a bifunctional unsaturated epoxy carboxylate compound, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, and a reactive urethane compound obtained by reacting a diisocyanate compound are patented. It is described in Document 1.

  This reactive urethane compound has good flexibility and heat resistance as compared with conventional epoxy acrylate materials, but cannot exhibit the higher flexibility currently required.

  Furthermore, in a means for forming a reactive urethane compound by simply using another diol compound, which is a means for improving the flexibility of a general urethane compound, a significant decrease in heat resistance is observed, and the use for a solder resist, etc. The heat resistance and curability required for the above cannot be obtained.

Attempts have been made to add a rubber compound having two hydroxyl groups in the molecule for the purpose of imparting flexibility (Patent Document 2).
This makes it possible to exhibit relatively good flexibility, but the rubber compound has poor compatibility with the reactive urethane compound, and when a rubber compound is used in an amount sufficient to exhibit sufficient flexibility, the phase separation state End up. Even when the active energy ray-curable resin composition is blended with other compounds, a compatibility problem occurs.

  If a compatibility problem occurs, it will adversely affect the developability, specifically difficult to develop, difficult to form fine patterning, and the like. In addition, it is difficult to exhibit satisfactory characteristics with respect to heat resistance.

  In addition, there is an attempt to use a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, a polyester-based or polycarbonate-based diol, and a non-reactive urethane compound obtained by reacting a diisocyanate compound (Patent Literature). 3). However, this urethane compound does not have reactivity with active energy rays. For this reason, in order to obtain reactivity to active energy rays, that is, to obtain a fine patternable resin composition by optical drawing, it is necessary to use other reactive compounds in combination. Flexibility, heat resistance, etc. cannot be exhibited at a high level.

JP-A-9-52925 Japanese Patent Laid-Open No. 2003-147043 JP 2006-124681 A

  In the present invention, photo-patterning is possible, but heat resistance such as solder at the time of substrate manufacture and heat generation of elements used for the substrate, reliability of maintaining high insulation for a long time, plating treatment, etc. The aim is to provide a material that combines the flexibility and toughness required of flexible substrates and the like at a high level without impairing the basic characteristics required of solder resists such as chemical resistance to chemical treatment.

  In order to solve the above problems, the present inventors reacted an epoxy compound having two epoxy groups in one molecule with a compound having at least one ethylenically unsaturated group and one carboxyl group in the molecule. It is obtained by reacting an unsaturated epoxycarboxylate compound obtained, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, a polyester diol compound, and a compound having two isocyanate groups in one molecule. A polyurethane compound was found. Furthermore, the acid-modified compound, a resin composition containing them, and a cured product thereof were found.

That is, the present invention comprises reacting an epoxy compound (ii) having two epoxy groups in one molecule with a compound (ii) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule. Unsaturated epoxycarboxylate compound (a), compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, polyester diol compound (c), and two isocyanate groups in one molecule The present invention relates to a polyurethane compound (A) obtained by reacting a compound (d) having
Furthermore, this invention relates to the acid-modified polyurethane compound (B) obtained by making a polybasic acid anhydride (e) react with a polyurethane compound (A).

The present invention further relates to an active energy ray-curable resin composition containing the polyurethane compound (A) and / or the acid-modified polyurethane compound (B).
The present invention further relates to an active energy ray-curable resin composition containing a reactive compound (C) other than the polyurethane compound (A) and the acid-modified polyurethane compound (B).

Furthermore, this invention relates to the said active energy ray hardening-type resin composition which is a film forming material.
Furthermore, the present invention relates to the active energy ray-curable resin composition, which is a film forming material for the purpose of electrical insulation.
Furthermore, this invention relates to the said active energy ray hardening-type resin composition for using for a permanent resist.
Furthermore, this invention relates to the hardened | cured material of the said active energy ray hardening-type resin composition.

  The polyurethane compound of the present invention, the acid-modified compound thereof, the specific resin composition containing them, and the cured product thereof can be subjected to photo-patterning, but the heat of solder and the like during the production of the substrate and the heat generation of the element used for the substrate Flexible substrates without compromising the basic characteristics required of solder resists, color resists, etc., such as heat resistance that can withstand high temperatures, reliability of maintaining high insulation for a long time, and chemical resistance to chemical treatments such as plating It is a material having both flexibility and toughness required for a high degree, and can be particularly suitably used for a film forming material required for flexibility, for example, a solder resist for a flexible substrate.

The reactive polyurethane compound (A) of the present invention is a compound having at least one ethylenically unsaturated group and one carboxyl group in one molecule in the epoxy compound (i) having two epoxy groups in one molecule. Unsaturated epoxycarboxylate compound (a) obtained by reacting (ii), compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, polyester diol compound (c) and one molecule And a compound (d) having two isocyanate groups can be reacted.
That is, the polyurethane compound (A) of the present invention is produced by two reaction steps. First, an epoxy compound (i) having two epoxy groups in one molecule and a compound (ii) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule are reacted to produce an unsaturated epoxy. In this step, the carboxylate compound (a) is obtained. In the present invention, this step is referred to as a carboxylation step.
Subsequently, the unsaturated epoxycarboxylate compound (a) thus obtained, the compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule, the polyester diol compound (c) and two in one molecule This is a step of reacting the compound (d) having an isocyanate group. In the present invention, this step is a urethanization step.

  The unsaturated epoxycarboxylate compound (a) obtained in the carboxylation step is a carboxylate having two or more ethylenically unsaturated groups and two hydroxyl groups derived from the epoxy group of the epoxy compound (i) in one molecule. A compound.

  In the subsequent urethanization step, two hydroxyl groups of the unsaturated epoxycarboxylate compound (a), two hydroxyl groups of the polyester diol compound (c), and a compound (d) having two isocyanate groups in one molecule are obtained. A polyurethane compound (A) is obtained by reaction.

  The epoxy compound (i) having two epoxy groups in one molecule used for the production of the polyurethane compound (A) of the present invention is particularly limited as long as it has two epoxy groups in one molecule. Not. A monofunctional epoxy compound cannot adjust the molecular weight of the polyurethane compound (A) obtained by the urethanization step, and a trifunctional or higher epoxy compound has a multi-branched structure, so that a suitable cured material property can be obtained. Is difficult.

  Examples of the epoxy compound (i) include bisphenol diglycidyl ethers such as bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether, bisphenol fluorenediglycidyl ether, and biphenol diglycidyl ether. , Aromatic diglycidyl ether compounds such as biphenyl glycidyl ethers such as tetramethylbiphenol glycidyl ether; alkyl diol diglycidyl ethers such as hexanediol diglycidyl ether, and alkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether Cyclohexane diol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, etc. Saturated hydrocarbon diglycidyl ether compounds such as alkyl diol diglycidyl ethers; 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd.), 1,2 , 8,9-diepoxy limonene (Delcel Chemical Co., Ltd. Celoxide 3000), and so-called bifunctional alicyclic epoxy compounds.

  Of these, aromatic diglycidyl ether compounds are preferred because they have good heat resistance.

  Further, as the epoxy compound (i) having two epoxy groups in one molecule, those having no hydroxyl group are preferable. This is because the unsaturated epoxycarboxylate compound (a) obtained in the epoxycarboxylation step becomes a trifunctional or higher functional polyol compound and it becomes difficult to control the molecular weight of the polyurethane compound (A).

  The compound (ii) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule used in the production of the polyurethane compound (A) of the present invention is an ethylenically unsaturated group. The purpose is to introduce a saturated group and convert the epoxy compound (i) into a diol compound capable of reacting with an isocyanate group. The number of ethylenically unsaturated groups of the compound (ii) is preferably 1 to 4.

Examples of the compound (ii) include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or unsaturated groups other than saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives. The reaction material with a group containing monoglycidyl compound is mentioned.
Examples of the (meth) acrylic acids include (meth) acrylic acid, β-styryl (meth) acrylic acid, β-furfuryl (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, (Meth) acrylic acid dimers, saturated or unsaturated dibasic acid anhydrides and half-esters which are equimolar reactants of (meth) acrylate derivatives having one hydroxyl group per molecule, saturated or unsaturated And half-esters which are equimolar reaction products of dibasic acid and monoglycidyl (meth) acrylate derivatives.

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

  As the compound (ii) having both one or more ethylenically unsaturated groups and one carboxyl group in one molecule, those having no hydroxyl group in the compound are preferable.

  In the carboxylation step, the compound (ii) is preferably 90 to 120 equivalent% relative to 1 equivalent of the epoxy compound (i). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the compound (ii) charged is larger than this, the compound (ii) having a carboxyl group remains, which is not preferable. If the amount is too small, unreacted epoxy compound (i) remains, which causes a problem in the stability of the resin.

  In the carboxylation step, the reaction can be carried out without solvent or diluted with a solvent. When a solvent is used, it is not particularly limited as long as it is an inert solvent for the carboxylation reaction. In addition, it is preferable to use an inert solvent in the urethanization step, which is the next step, or in the acid addition step described later as necessary.

  When a solvent is used, the amount used should be appropriately adjusted depending on the viscosity and use of the resulting resin, but preferably the solid content is 99 to 30% by weight, more preferably 99 to 45% by weight. It may be used so that When the compound used for the reaction has a high viscosity, the viscosity is suppressed and the reaction proceeds suitably.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, petroleum ether, white gasoline, and mixtures thereof. Solvent naphtha etc. are mentioned. Further, ester solvents, ether solvents, and ketone solvents may be used.

  Examples of the ester solvent 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- or polyalkylene glycol monoalkyl ether monoacetates such as acetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, glutar such as dimethyl glutarate Dialkyl succinates such as dialkyl succinate and dimethyl succinate Polycarboxylic acid dialkyl esters of dialkyl adipates such as dimethyl adipate and the like.

  Examples of the ether solvent 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, if the reaction is inert, a reactive compound (C) described later may be used alone or in combination as a solvent. In this case, it can be used as it is as a curable composition.

In the carboxylation step, it is preferable to use a catalyst in order to accelerate the reaction. When the catalyst is used, the amount used is 0.1 to 10% by weight based on the total amount of the reactants, that is, the epoxy compound (i), the compound (ii) and the solvent when the solvent is used. Degree. In this case, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
Examples of the catalyst include general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, and zirconium octoate. Etc.

  In addition, a thermal polymerization inhibitor may be used. Examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-t-butyl. It is preferable to use -4-hydroxytoluene.

  In the carboxylate conversion step, the end point is when the acid value of the sample is 5 mg · KOH / g or less, preferably 2 mg · KOH / g or less, while sampling appropriately.

Next, the urethanization step will be described in detail.
The compound (b) having both two hydroxyl groups and one or more carboxyl groups in one molecule used for the production of the polyurethane compound (A) of the present invention introduces a carboxyl group into the polyurethane compound (A), It is soluble in an alkaline aqueous solution necessary for patterning. The number of carboxyl groups in the compound (b) is preferably 1 to 4.

  As the compound (b), for example, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid and the like are preferable, and dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable in consideration of availability of raw materials.

By using the polyester diol compound (c) for the production of the polyurethane compound (A) of the present invention, sensitivity, heat resistance, chemical resistance, etc. and flexibility can be fused at a high level.
The polyester diol compound (c) is characterized by having two hydroxyl groups in one molecule and further having an ester bond in the main skeleton.

  Examples of the polyester diol compound (c) include diol dicarboxylic acid ester diols in which a diol compound and dicarboxylic acids are connected by an ester bond, polylactone diols obtained by ring-opening polymerization of cyclic esters with a diol compound, alkyls Examples thereof include polycarbonate diols having a carbonate bond obtained by a reaction between a carbonate and a diol compound, and polyester diols obtained by combining these in a complex manner. These diol compounds are not particularly limited as long as they are compounds having two hydroxyl groups other than the unsaturated epoxycarboxylate compound (a) and the compound (b).

  Diol dicarboxylic acid ester diols in which a diol compound and a dicarboxylic acid compound are connected by an ester bond include, for example, ethylene glycol adipic acid ester diol, propylene glycol adipic acid ester diol, butylene glycol adipic acid ester diol, neopentyl glycol adipic acid ester Diol, methylpentanediol adipate diol, hexanediol adipate diol, ethylene glycol sebacate diol, hexanediol dodecanedioate diol, ethylene glycol phthalate diol, ethylene glycol azelate diol, etc. .

  Examples of the polylactone diol compound obtained by ring-opening polymerization of cyclic esters include polybutyrolactone diol, polyvalerolactone diol, polycaprolactone diol, and the like.

  Examples of the polycarbonate diol compound include polypropylene carbonate diol, polybutylene carbonate diol, polyhexamethylene carbonate diol, polyoctamethylene carbonate diol, polynonane diol carbonate diol, polycyclohexane carbonate diol, polycyclohexane dimethanol carbonate diol, and the like. .

  Among these, as the polyester diol compound (c), polycaprolactone diols and polycarbonate diols are particularly preferable since they exhibit suitable cured product properties. In particular, polycarbonate diols are more preferable because they can induce a polyurethane compound (A) that gives a tough cured film.

  The preferred molecular weight range of the polyester diol compound (c) is preferably in the range of 250 to 5000, more preferably 650 to 3000. When the molecular weight is smaller than this range, the effect of imparting flexibility is low, and when it is larger than this range, the heat resistance is greatly reduced.

  The compound (d) having two isocyanate groups in one molecule used for the production of the polyurethane compound (A) of the present invention is an unsaturated epoxy carboxylate compound (a), a compound (b), a polyester diol compound ( Used in the urethanization step with the hydroxyl group of c) to give the polyurethane compound (A) suitable flexibility.

  Examples of the compound (d) include aliphatic linear diisocyanates, alicyclic diisocyanates, aromatic isocyanates, and the like.

  Examples of the aliphatic linear diisocyanates include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the alicyclic diisocyanates include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated methylene bisphenylene diisocyanate.

  Examples of aromatic diisocyanates include tolylene diisocyanate, xylylene diisocyanate, methylene bisphenylene diisocyanate, and the like.

  Of these, aliphatic or alicyclic diisocyanates are preferred for increasing flexibility, and aliphatic linear diisocyanates are particularly preferred.

  The urethanization step includes an unsaturated epoxy carboxylate compound (a), a compound having two hydroxyl groups and one or more carboxyl groups in one molecule (b), a mixture of polyester diol compound (c), and one molecule. It is carried out by mixing the compound (d) having two isocyanate groups.

In the production of the polyurethane compound (A), (number of moles of unsaturated carboxylate compound (a) + number of moles of compound (b) + number of moles of polyester diol compound (c)) ÷ (number of moles of isocyanate compound (d)) ), 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 1.15 to 1.6. That is, from the viewpoint of the storage stability of the polyurethane compound (A), in the urethanization step, at least the number of hydroxyl groups is larger than that of isocyanate groups, and the isocyanate groups are not finally left.
Furthermore, if it is larger than this range, the molecular weight of the resulting polyurethane compound (A) becomes too small, making it difficult to obtain a tough cured product. If it is too small, the molecular weight of the resulting polyurethane compound (A) will be large. In some cases, the developability may be adversely affected.

  In the production of the polyurethane compound (A) of the present invention, the preferred weight ratio of the weight of the carboxylate compound (a), the weight of the compound (b), the weight of the polyester diol compound (c), and the weight of the compound (d) is the total weight. 5 to 65 parts by weight of the carboxylate compound (a), 5 to 25 parts by weight of the compound (b), 0.5 to 60 parts by weight of the polyester diol compound (c), and compound (d) Is 20-40 parts by weight. Within this range, a polyurethane compound (A) having photo patterning and developability with an aqueous alkali solution and having characteristics suitable as a resist material is obtained, and has particularly high heat resistance, chemical resistance and excellent flexibility. A cured product having a well-balanced dimension can be obtained.

This suitable range is slightly different depending on the type of the polyester diol compound (c) to be combined.
For example, in the case of polycaprolactone diols having relatively good flexibility, the above-mentioned balance is more easily achieved when the carboxylate compound (a) is increased while the polyester diol compound (c) is decreased. That is, the carboxylate compound (a) is 38 to 60 parts by weight, more preferably 45 to 55 parts by weight, the compound (b) is 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, and the polyester diol compound (c). Is 0.5 to 30 parts by weight, more preferably 1 to 15 parts by weight, and the compound (d) is 20 to 40 parts by weight, more preferably 25 to 30 parts by weight.

  In the case of relatively rigid polycarbonate diols, the above balance is more likely to be exhibited when the carboxylate compound (a) is reduced and the polyester diol compound (c) is increased. That is, the carboxylate compound (a) is 15 to 60 parts by weight, more preferably 20 to 45 parts by weight, the compound (b) is 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, and the polyester diol compound (c). Is 3 to 55 parts by weight, more preferably 10 to 40 parts by weight, and the compound (d) is 20 to 40 parts by weight, more preferably 20 to 30 parts by weight.

  The urethanization step can be reacted with no solvent or diluted with a solvent. When using a solvent, it is not particularly limited as long as it is an inert solvent for the urethanization reaction.

  In the case of using a solvent, the amount used should be appropriately adjusted depending on the viscosity and usage of the resin to be obtained. Preferably, the solid content is 99 to 30% by weight, more preferably 90 to 45% by weight. % May be used. It is also possible to use the solvent used in the carboxylation step as it is, provided that it is inert in both steps.

  As this solvent, the thing similar to the solvent illustrated in the said carboxylate-ized process is mentioned, for example. Moreover, if inert to reaction, you may use the reactive compound (C) mentioned later as a solvent individually or in mixture. In this case, it can be used as it is as a curable composition.

  In the urethanization step, a thermal polymerization inhibitor or the like may be used, and the same compounds as those exemplified in the 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 a catalyst is used, the amount used is about 0.01 to 1% by weight with respect to the total amount of reactants. Examples of the catalyst include general basic catalysts, for example, Lewis base catalysts such as tin ethylhexanoate.

  The reaction temperature in the urethanization step is 40 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

The reaction in the urethanization step is regarded as the reaction end point when almost no isocyanate groups remain. The end point of the reaction is determined by observing a peak around 2250 cm ⁻¹ derived from an isocyanate group by an infrared absorption spectrum measurement method or by a titration method shown in JIS K1556: 1968 or the like.

  The preferred molecular weight range of the carboxylate compound (A) of the present invention thus obtained is in the range of 1000 to 30000 in terms of polystyrene-equivalent weight average molecular weight in GPC, more preferably in the range of 3000 to 20000. If the molecular weight is smaller than this, the toughness of the cured product will not be sufficiently exhibited, and if it is larger than this, not only will the viscosity increase and coating will become difficult, but the developability will also decrease. Cheap.

  The present invention also includes an acid-modified polyurethane compound (B) obtained by reacting the reactive polyurethane compound (A) with a polybasic acid anhydride (e) as necessary. As a result, the acid value required for alkali development can be added as appropriate according to the required properties of the resin as well as the compound (b) having two hydroxyl groups and one or more carboxyl groups in one molecule. It becomes.

In the present invention, this reaction step is referred to as an acid addition step.
Next, the acid addition step will be described in detail. The acid addition step is a step in which a polybasic acid anhydride (e) is reacted with the hydroxyl group remaining after the urethanization reaction to introduce a carboxyl group via an ester bond. Therefore, acid addition cannot be performed beyond the equivalent of the hydroxyl groups remaining after the urethanization step.

  Examples of the polybasic acid anhydride (e) include compounds having a cyclic acid anhydride structure in one molecule, and succinic anhydride (SA) from the viewpoint of alkali aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Phthalic anhydride (PAH), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or Maleic anhydride and the like are preferred.

  An acid addition process is performed by adding a polybasic acid anhydride (e) to the said polyurethane compound (A). The amount of the polybasic acid anhydride (e) used is required for the set value of the polyurethane compound (A), that is, the acid value derived from the compound (b), the amount of hydroxyl groups remaining, and the polyurethane compound (A). What is necessary is just to change suitably based on an acid value.

  When the polyurethane compound (A) and / or acid-modified polyurethane compound (B) of the present invention is used as an alkali development resist, the solid content acid value of the finally obtained polyurethane compound (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, it is possible to achieve a balance between good solubility of the non-irradiated part of active energy ray and insolubility of the active energy ray irradiated part.

In the acid addition step, a catalyst is preferably used to promote the reaction, and the amount used is about 0.1 to 10% by weight based on the total amount of the reactants. In this case, 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, chromium octoate, zirconium octoate and the like.

  In the acid addition step, the reaction can be performed without solvent or diluted with a solvent. When a solvent is used, the solvent is not particularly limited as long as it is an inert solvent in the acid addition reaction. Moreover, when it manufactures using a solvent in the urethanization process which is a previous process, if both reactions are inert, what is necessary is just to perform an acid addition reaction, without removing a solvent.

The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and usage of the resin obtained, but preferably the solid content is 90 to 30% by weight, more preferably 80 to 50% by weight. Use it.
As the solvent, the same solvents as those exemplified in the carboxylation reaction and urethanization step may be used.

  Moreover, if inert to reaction, you may use the reactive compound (C) mentioned later as a solvent individually or in mixture. In this case, it can be used as it is as a curable composition.

  In the acid addition step, a thermal polymerization inhibitor or the like may be used, and the same compounds as those exemplified in the carboxylation step and the urethanization step can be used.

  The reaction in the acid addition step is appropriately sampled, and the end point is determined when the acid value of the reaction product is in the range of plus or minus 10% of the set acid value.

  The active energy ray-curable resin composition of the present invention contains a polyurethane compound (A) and / or an acid-modified polyurethane compound (B). Furthermore, the resin composition containing reactive compounds (C) other than a component (A) and a component (B) is preferable.

  Examples of the reactive compound (C) include radical-reactive acrylates, cation-reactive epoxy compounds, and vinyl compounds that are sensitive to both.

  Examples of the radical reaction type acrylates include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.

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

  Examples of the polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, ethylene 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 (meta) ) Acrylate, hydrogenated bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, hydroxybivalic acid neope Di (meth) acrylate of ε-caprolactone adduct of til glycol, poly (meth) acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, Triacetylolpropane tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate or its ethylene oxide adduct, dipentaerythritol hexa (meth) acrylate or its Examples include ethylene oxide adducts.

  The cation-reactive epoxy compounds are not particularly limited as long as they have an epoxy group including the epoxy compound (i). For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether Bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (such as “Syracure UVR-6110” manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4 -Epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (such as "Celoxide 3000" manufactured by Daicel Chemical Industries), allyl Chlohexene 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-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.

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

  Further, the reactive compound (C) has a functional group sensitive to active energy rays and a urethane bond in the same molecule, and other urethane acrylates excluding the polyurethane compound (A) and acid-modified polyurethane compound (B), Similarly, a polyester acrylate having a functional group sensitive to active energy rays and an ester bond in the same molecule, an epoxy acrylate derived from an epoxy compound and having a functional group sensitive to active energy rays in the same molecule, these bonds You may use the oligomer etc. which are used in combination.

  Among these, the reactive compound (C) is preferably a radical curable acrylate. In the case of the cation reaction type, since the carboxylic acid and the epoxy group react with each other, it is necessary to use a two-component mixed type for preparation at the time of use.

  Other components may be appropriately added to the active energy ray-curable resin composition of the present invention depending on applications.

The active energy ray-curable resin composition of the present invention contains 97 to 5% by weight, preferably 87 to 10% by weight, of the polyurethane compound (A) and / or the acid addition type polyurethane compound (B) in the composition. The reactive compound (C) other than (A) and component (B) is contained in an amount of 3 to 95% by weight, preferably 3 to 90% by weight. For the purpose of adapting to various applications, other components may be included up to about 75% by weight as necessary.
Examples of other components include a photopolymerization initiator, other additives, a pigment material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability.

Examples of the photopolymerization initiator that may be contained in the active energy ray-curable resin composition of the present invention include radical photopolymerization initiators and cationic photopolymerization initiators.
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-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthrone such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Laquinones; 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, 4 Benzophenones such as 2,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

  Cationic photopolymerization initiators include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, Lewis acid phosphonium salts, other halides, triazine initiators, borate initiators, other Examples include 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.), etc. Is mentioned.
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 (such as Cyracure UVI-6990 manufactured by Union Carbide), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide), and the like. .
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 (Trigonal PI manufactured by AKZO), 2,2-dichloro-1- (4- And phenoxyphenyl) ethanone (Sandray 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.), and the like.
Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) triazine, 2,4-bis (trichloromethyl) -6- (4′-methoxyphenyl) triazine (such as Triazine A manufactured by Panchi). 2,4-bis (trichloromethyl) -6- (4′-methoxystyryl) triazine (such as Triazine PMS manufactured by Panchim), 2,4-bis (trichloromethyl) -6-piperonyltriazine (manufactured by Panchim) Triazine PP, etc.), 2,4-bis (trichloromethyl) -6- (4′-methoxynaphthyl) triazine (Trizine B, etc. manufactured by Panchim), 2- [2 ′-(5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 -(2'-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the baud rate initiator include NK-3876, NK-3881, and the like (both manufactured by Nippon Photosensitizer).
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-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydro Chloride (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, etc. manufactured by Ciba Geigy), bis (eta-5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyridin-1-yl) Eniru] titanium (Ciba Geigy Corp. CGI-784, etc.), and the like.

  Furthermore, 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, and one type of each initiator may be used alone, or two or more types may be used in combination.

  Of these, radical photopolymerization initiators are particularly preferred in view of the properties of the urethane compound of the present invention.

  Furthermore, the active energy ray-curable resin composition of the present invention may appropriately contain a curing agent according to the intended use. The curing agent is used to obtain a strong cured film by a reaction with an acidic group contained, particularly in a material intended for electrical insulation.

  Examples of the curing agent include epoxy compounds other than the reactive compound (C), and among them, an epoxy compound containing two or more epoxy groups in one molecule is preferable. This is because a stronger cured product can be obtained than using a monofunctional epoxy compound. The epoxy equivalent of these epoxy compounds is preferably in the range of 150 to 450 g / eq, more preferably 180 to 350 g / eq. When the epoxy equivalent is smaller than this, the obtained cured product tends to be fragile, and when it is larger than this, the resulting cured product tends to be weak because the number of crosslinking sites is reduced.

  The epoxy compound is arbitrarily selected depending on the purpose of use of the cured product and the required characteristics, and a known general epoxy compound can be arbitrarily used.

  Examples of the monofunctional epoxy compound include phenyl glycidyl ether and glycidyl (meth) acrylate.

  Examples of the epoxy compound having two or more epoxy groups in the molecule include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a dicyclopentadienephenol type epoxy resin, and a bisphenol-A type. Examples thereof include epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolak type epoxy resins, naphthalene skeleton-containing epoxy resins, glyoxal type epoxy resins, and heterocyclic epoxy resins.

Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by DIC Corporation), D.I. E. N438 (made by Dow Chemical Company), jER154 (made by Japan Epoxy Resin Co., Ltd.), EPPN-201, RE-306 (all made by Nippon Kayaku Co., Ltd.), etc. are mentioned.
Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), jER E1032H60 ( Japan Epoxy Resin Co., Ltd.).
Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by DIC Corporation), TACTIX-556 (manufactured by Dow Chemical Company), and the like.

  Examples of the bisphenol type epoxy resin include jER828, jER1001 (all manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), NER- 1202, NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.), Bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.), NER-7403, NER-7604 (both manufactured by Nippon Kayaku Co., Ltd.), etc. Can be mentioned.

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000, NC-3000-H, NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), YX-4000 (Japan Epoxy Resin). Bixylenol type epoxy resin (manufactured by Co., Ltd.), YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
Examples of the bisphenol A novolak type epoxy resin include Epicron N-880 (manufactured by DIC Corporation), jER E157S75 (manufactured by Japan Epoxy Resin Corporation), and the like.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Corporation), and the like.
Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).
Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

  Among them, biphenol type epoxy resins are particularly effective in terms of flexibility, and for example, NC-3000, NC-3000-H, NC-3000-L, etc. are most preferable.

  When the epoxy compound is contained, the preferred blending amount is about 5 to 80% by weight, more preferably about 10 to 70% by weight of the solid content of the active energy ray-curable resin composition of the present invention. When the blending amount is less than this amount, the obtained cured product tends to be soft, and when it is too large, the curability and the like may be adversely affected due to the problem of balance with the following epoxy curing agent.

Other additives that may be contained in the active energy ray-curable resin composition of the present invention include, for example, thermosetting catalysts such as melamine, thixotropic agents such as aerosil, silicone-based and fluorine-based leveling agents, Examples thereof include defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, and flame retardants for imparting flame retardancy.
In particular, when used as a film-forming material for the purpose of electrical insulation, it is preferable to use it together with a flame retardant. As the preferred flame retardant, known general ones can be used, such as brominated epoxy resins, halogen flame retardants such as bromodiphenyl ether, phosphate ester resins such as phosphazene resins and triphenyl phosphate, dihydro-9-oxa-phosphaphenanthrene. Organophosphorus flame retardants such as -10-oxide derivatives, metal hydroxide flame retardants such as magnesium hydroxide, and inorganic flame retardants such as red phosphorus and antimony trioxide are preferably used.

Examples of the pigment material that may be contained in the active energy ray-curable resin composition of the present invention include colored pigments for coloring purposes and extender pigments for non-coloring purposes.
Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, inorganic pigments such as carbon black, and titanium oxide.
Examples of the extender pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

  Furthermore, you may contain resin (what is called an inert polymer) which does not show the reactivity to an active energy ray. Examples of the resins include other epoxy resins except the epoxy resin as the curing agent, phenol resin, urethane resin, polyester resin, ketone formaldehyde resin, cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin. Natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof may be contained in the active energy ray-curable resin composition of the present invention. These are preferably used in the active energy ray-curable resin composition in a range of up to 40% by weight.

  In particular, when the polyurethane compound (A) and / or the acid addition type polyurethane compound (B) is used for solder resist applications, the combined use of an epoxy resin is preferable. By further carboxylating the remaining carboxyl groups after curing with active energy rays, a strong cross-linked structure is formed, and the cured product is excellent in water resistance and hydrolyzability.

  The volatile solvent which may be contained in the active energy ray-curable resin composition of the present invention is 50% by weight, more preferably 35% by weight in the resin composition for the purpose of adjusting the viscosity according to the purpose of use. It may be added in the range up to%.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Examples of the 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 rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

The present invention includes the use of the active energy ray-curable resin composition as a film-forming material for coating the surface of a substrate. That is, for example, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, adhesives and adhesives for laminating and optical disks, etc. Examples thereof include an adhesive material such as an agent, a resist material such as a solder resist, an etching resist, and a micromachine resist.
Furthermore, 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, also corresponds to the film-forming material. .

  The present invention includes use of the active energy ray-curable resin composition as a film-forming material for the purpose of electrical insulation. That is, materials that require electrical insulation such as solder resist materials for circuit boards, insulating molding materials, interlayer insulating materials, semiconductor protective film materials, and wiring coating materials fall under this category.

  In the present invention, 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 drawing is performed by utilizing the physical difference between an irradiated part and an unirradiated part. The use of the active energy ray-curable resin composition as an active energy ray-sensitive resist material to be used is also included. That is, the irradiation part or the non-irradiation part is used for the purpose of removing and drawing by some method, for example, dissolving with a solvent or an alkaline solution.

  The active energy ray-curable resin composition used for the permanent resist is also included in the present invention. Permanent resist is not used on the premise that the resist material is stripped after drawing, but the purpose and function of the resist material are maintained without being stripped until actual use. Is.

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

  In addition, taking advantage of the property of being able to obtain a toughened cured product while being flexible, the effect of the present invention can be maximized when used for insulating materials for flexible substrates that require flexibility, This is a suitable application.

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

  The cured product obtained by irradiating the active energy ray-curable resin composition with active energy rays and curing it is also included in the present invention.

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

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent (WPE): Measured by a method according to JIS K 7236: 2001.
2) Total chlorine: Measured by a method according to JIS K 7243-3: 2005.
3) Acid value: measured by a method according to JIS K 0070: 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: Preparation of carboxylate compound (a) (carboxylation step)
As bisphenol-A type epoxy resin (i), 1840 g of RE-310S (WPE = 184 g / eq, manufactured by Nippon Kayaku Co., Ltd.), one or more ethylenically unsaturated groups and one carboxyl group in one molecule 720 g of acrylic acid (abbreviation AA, Mw = 72), 30 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate (abbreviation PGMAc) as a solvent so that the solid content is 80%. And a carboxylate compound solution was obtained by reaction at 100 ° C. for 24 hours.

  The reaction was terminated when the acid value in terms of solid content reached 1.8 mg · KOH / g. The acid value was measured with a reaction solution and converted into an acid value as a solid content. Moreover, when the epoxy value was measured, it was 13 kg / eq, and it was also confirmed that the epoxy group was sufficiently reacted.

Example 1: Preparation of polyurethane compound (A) (urethanization step)
The amount of the carboxylate compound (a) solution obtained in Synthesis Example 1 in the reaction tank described in Table 1 (the stated value is a solid content conversion value), a compound having two hydroxyl groups and one or more carboxyl groups in one molecule As (b), dimethylolpropionic acid is described in Table 1, polyester diol compound (c), polyester diol described in Table 1 is described in Table 1, and propylene glycol monomethyl ether acetate (abbreviation PGMAc) is used as a solvent. 100 g of polyurethane compound (A) was added and dissolved with stirring so that the solid content was 50%. Further, 0.5 g of tin octoate as a catalyst and 0.1 g of hydroquinone as a thermal polymerization inhibitor were added and heated to 100 ° C. Thereafter, hexamethylene diisocyanate was added as a compound (d) having two isocyanate groups in one molecule described in Table 1 using a dropping funnel, and reacted. After completion of the dropping, the reaction was continued for 10 hours, and it was confirmed that there was no absorption peak derived from the isocyanate group in the infrared absorption spectrum to obtain a polyurethane compound (A). The results are also shown in Table 1.
In Examples 1-23 and thereafter, the polyurethane (A) was prepared by changing the isocyanate (d) from hexamethylene diisocyanate. Example 1-23 used trimethylhexamethylene diisocyanate, Example 1-24 used isophorone diisocyanate, and Example 1-25 used tolylene diisocyanate.

Comparative Example 1: Preparation of Comparative Polyurethane Compound Using the carboxylate compound (a) prepared in Synthesis Example 1, various urethane compounds in Table 1 were prepared in the same manner as in Example 1. The results are shown in Table 1.

[Table 1] Example 1, Comparative Example 1 (Preparation of Reactive Polyurethane Compound (A))

Abbreviations in the table:
(A + b + c) / d: ratio of the total number of moles of hydroxyl groups and the total number of moles of isocyanate contained in the reaction system AV: solid content acid value (mg · KOH / g): measured as a solution and measured as solid content Converted to value.
Mw: Weight average molecular weight measured using gel permeation chromatograph (polystyrene standard conversion value)
PCL500: Polycaprolactone diol (Placcel 205, manufactured by Daicel Chemical Industries) average molecular weight 500
PCL1000: polycaprolactone diol (Placcel 210, manufactured by Daicel Chemical Industries) average molecular weight 1000
PCL2000: Polycaprolactone diol (Placcel 220, manufactured by Daicel Chemical Industries) average molecular weight 2000
PCL4000: Polycaprolactone diol (Placcel 240, manufactured by Daicel Chemical Industries) average molecular weight 4000

PBA1000: Polybutanediol adipic acid ester diol (Polylite OD-X-240, manufactured by DIC Corporation) average molecular weight 1000
PCB1000: Polyhexanediol carbonate diol (Placcel CD CD210, manufactured by Daicel Chemical Industries) average molecular weight 1000
PCC1000: Polycyclohexanediol carbonate diol (Ethanacol UC-100, manufactured by Ube Industries, Ltd.) average molecular weight 1000
PCB2000: Polyhexanediol carbonate diol (Placcel CD CD220, manufactured by Daicel Chemical Industries) average molecular weight 2000
PBD1000: polybutadiene diol (Nisso PB G-1000, manufactured by Nippon Soda Co., Ltd.) average molecular weight 1000
PBH1000: Hydrogenated polybutadiene diol (Nisso PB GI-1000, manufactured by Nippon Soda Co., Ltd.) Average molecular weight 1000
PEG1000: Polyethylene glycol (PEG # 1000, manufactured by NOF Corporation) average molecular weight 1000
PBG1000: Polybutylene glycol (PTMG1000, manufactured by Mitsubishi Chemical Corporation) Average molecular weight 1000

Example 2: Preparation of acid-modified polyurethane compound (B) (acid addition step)
In the reaction vessel, the amount of the PGMAc solution of the polyurethane compound (A) obtained in Example 1 described in Table 2, and the acid anhydride described in Table 2 as the acid anhydride (d) are described in Table 2. (Calculated value of 90 mg · KOH / g as the solid content acid value) was added. Further, PGMAc having the same weight as the acid anhydride was added as a solvent so that the final solid content was 50%. As a catalyst, 0.2 g of triethylamine was added and dissolved by stirring.

  After dissolution, the mixture was heated to 100 ° C. with stirring and reacted for 50 hours to obtain an acid-modified reactive polyurethane compound (B). After completion of the reaction, the acid value was measured to confirm the completion of the reaction. The results are shown in Table 2.

Comparative Example 2: Preparation of Comparative Acid Addition Type Urethane Compound Using the other reactive urethane compound prepared in Comparative Example 1, the urethane compound was prepared in the same manner as in Example 2 to prepare a urethane compound. The results are shown in Table 2.

[Table 2] Example 2, Comparative Example 2 (Preparation of acid-modified reactive polyurethane compound (B))

Example 3: Characteristic evaluation of polyurethane compound (A) and acid-modified polyurethane acrylate (B) (appropriate evaluation as a solder resist composition for flexible substrates)
54.4 g of the polyurethane compound (A) obtained in Example 1 or the acid-modified polyurethane compound (B) obtained in Example 2 and HX-220 (trade name: Nippon Kayaku) as the reactive compound (C) 3.5 g of diacrylate monomer), 4.7 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 0. 5 g, 14.8 g of cresol novolac type epoxy resin (trade name: EPPN-201, manufactured by Nippon Kayaku Co., Ltd.) as a curing component, 1.0 g of melamine as a thermosetting catalyst, and diethylene glycol monomethyl ether monoacetate as a concentration adjusting solvent Was added and dispersed uniformly to obtain a resist resin composition.

  The resulting composition has a dry film thickness of about 20 microns on a copper-laminated polyimide film (copper circuit thickness 12 microns, polyimide film thickness 25 microns) molded with various test patterns using the silk screen method. It adjusted so that it might coat. After coating, the solvent was volatilized by passing through a hot air drying furnace at a temperature of 70 ° C.

Subsequently, a Kodak step tablet No. for estimating the mask or sensitivity on which a circuit pattern was drawn using an ultraviolet exposure apparatus (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% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area. Further, the substrate was washed and dried with water, and then subjected to a heat curing reaction in a hot air dryer at 150 ° C. for 60 minutes to obtain a flexible substrate.
Various evaluations were performed with this flexible substrate. The results are shown in Table 3.

Comparative Example 3: Resist Suitability Evaluation of Comparative Resin Composition The polyurethane compound or acid-modified polyurethane compound obtained in Comparative Example 1 or Comparative Example 2 was used as the polyurethane compound (A) or acid-modified polyurethane compound of Example 3 ( A similar test was conducted using the test instead of B). The evaluation method and evaluation criteria were also performed in the same manner.
The results are shown in Table 3.

  Each item of the evaluation items will be described in detail.

Sensitivity evaluation (abbreviation in the table: sensitivity)
Sensitivity was determined based on how many density portions remained in the exposed portion that passed through the step tablet during development for 60 seconds. Since the higher step number (value) is the dark portion of the tablet, it is determined that the sensitivity is high (unit: step).

Evaluation of developability (abbreviation in the table: developability)
The developability was evaluated based on the so-called break time (unit: second) until the pattern shape portion was completely developed when the exposed portion that passed through the pattern mask was developed. A suitable break time is about 20 to 50 seconds.

Curability evaluation (abbreviation in the table: curability)
The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C. The evaluation method was based on JIS K5600-5-4: 1999.

Folding resistance evaluation (abbreviation in the table: folding resistance)
The test was carried out according to JIS C-5016 8.7: 1994. The pattern film on which the cured resist film was formed was repeatedly bent using a folding tester. The evaluation was performed with the number of bendings until the circuit was disconnected.
For evaluation, six samples were prepared for each sample and expressed as an average value.
Bending test load: 4.9N
Bending curvature: 0.38R, 0.254mm
Bending speed: 175 times / min Evaluation criteria: It is judged that the one having a larger number of repetitions until disconnection has superior folding resistance.

Solder heat resistance evaluation (abbreviation in the table: heat resistance)
The test was performed according to JIS C-5016 10.3: 1994. Using a pattern film on which a cured resist film was formed, the film was immersed three times in a heated solder bath. After immersion, the flexible substrate was subjected to a cross-cut peel test to evaluate the peel condition.
Solder bath temperature: 260 ° C
One immersion time: 60 seconds Evaluation criteria: The total number of grids (100) was used as the denominator, and the number of remaining grids was shown in the numerator. An example is shown below.
100/100 No peeling 50/100 Half peeled 0/100 All peeled

Insulation reliability evaluation (abbreviation in the table: reliability)
A voltage of 100 V was applied to a comb-type pattern film having a line / space ratio of 100 microns / 100 microns, and the time until the resistance value fell below 10 megohm was measured by placing it in a constant temperature bath at 120 ° C. and 85% relative humidity. .
Evaluation criteria:
It is determined that the longer the time, the better the insulation reliability.

[Table 3] Example 3, Comparative Example 3: Evaluation of resist suitability for flexible substrate

Summarizing the above results, the polyurethane compound using the polyester diol contained in the active energy ray-curable resin composition of the present invention or its acid-modified polyurethane compound gives sensitivity, developability, curability, folding resistance. It was possible to obtain the resin composition having the properties which are contradictory to each other, such as property, heat resistance, and insulation reliability, at a high level in a well-balanced manner.
In view of this characteristic, it is clear that the (acid-modified) polyurethane compound of the present invention and the active energy ray-curable resin composition containing the same can be used particularly suitably as a solder resist for a flexible substrate.

  The polyurethane compound of the present invention, a composition containing the polyurethane compound, and a cured product thereof are materials having a well-balanced high level of sensitivity, developability, curability, folding resistance, heat resistance, and insulation reliability, which are conflicting properties. Yes, it can be suitably used as a resist material such as a resist material for flexible substrates, a color resist for flexible displays, and a spacer resist.

Claims (8)

Unsaturated epoxy obtained by reacting epoxy compound (i) having two epoxy groups in one molecule with compound (ii) having both one or more ethylenically unsaturated groups and one carboxyl group in one molecule Carboxylate compound (a), compound (b) having both two hydroxyl groups and one or more carboxyl groups in one molecule, mixture of polyester diol compound (c), and compound having two isocyanate groups in one molecule (D) and (number of moles of unsaturated epoxycarboxylate compound (a) + number of moles of compound (b) + number of moles of polyester diol compound (c)) ÷ (number of moles of isocyanate compound (d)) A polyurethane compound (A) obtained by reacting in the range of 1.05-2. An acid-modified polyurethane compound (B) obtained by reacting the polyurethane compound (A) according to claim 1 with a polybasic acid anhydride (e). An active energy ray-curable resin composition comprising the polyurethane compound (A) according to claim 1 and / or the acid-modified polyurethane compound (B) according to claim 2. The active energy ray-curable resin composition according to claim 3, further comprising a reactive compound (C) other than the polyurethane compound (A) according to claim 1 and the acid-modified polyurethane compound (B) according to claim 2. The active energy ray-curable resin composition according to claim 3 or 4, which is a film forming material. 6. The active energy ray-curable resin composition according to claim 5, wherein the film-forming material according to claim 5 is a film-forming material intended for electrical insulation. The active energy ray-curable resin composition according to any one of claims 3 to 6, for use in a permanent resist. Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 3-7.