JP6744233B2 - Polyurethane compound, active energy ray-curable resin composition containing the same and use thereof - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition containing a polyurethane compound (A) and/or the acid-modified polyurethane compound (B), and a cured product thereof. Particularly, active energy ray curing containing a polyurethane compound (A) and/or the acid-modified polyurethane compound (B) which can be suitably used as a resist material for a flexible substrate, a color resist material for a flexible display, a resist material such as a spacer resist, etc. Mold resin composition and cured product thereof.

2. Description of the Related Art In recent years, with the miniaturization of electronic information devices, the use of so-called flexible printed boards has increased due to their characteristics such as lightness, thinness, and flexibility as circuit boards.
Since the flexible printed circuit board is literally flexible, the material used for this has high sensitivity, adhesion, scratch resistance, high mechanical, thermal, and electrical properties while possessing the characteristics of optical patterning by alkali development. It is required to have a strong film forming ability with high flexibility capable of following a flexible substrate while having necessary properties such as strength.

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

On the other hand, in order to impart flexibility, it has been achieved by conservatively introducing a reactive group into the flexible main chain, that is, by appropriately reducing the crosslinking density.
As described above, these characteristics are contradictory to each other, and a solder resist material such as a flexible substrate is required to be a material that fuses these characteristics in a high dimension. Conventionally, an epoxy acrylate material has been mainly used, but this material has excellent chemical resistance, heat resistance, and other characteristics, but has insufficient flexibility. Therefore, it is difficult to obtain a tough film that has flexibility and 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 Reference 1.

This reactive urethane compound has good flexibility and heat resistance as compared with the conventional epoxy acrylate-based material, but cannot exhibit the higher flexibility required at present.

Further, in a means for forming a reactive urethane compound by simply using another diol compound in combination, which is a means for improving the flexibility of a general urethane compound, a remarkable decrease in heat resistance is observed, and it is used for a solder resist or the like. The required heat resistance and curability cannot be obtained.

Further, an attempt has been made to add a rubber compound having two hydroxyl groups in the molecule for the purpose of imparting flexibility (Patent Document 2).
As a result, relatively good flexibility can be exhibited, but the rubber compound has poor compatibility with the reactive urethane compound, and when the amount of the rubber compound is sufficient to exhibit sufficient flexibility, the phase separation state Will be. Even when the active energy ray-curable resin composition is blended with other compounds, the compatibility problem occurs.

When the compatibility problem occurs, it has a bad influence on the developability, specifically, it is difficult to develop, and it is difficult to form fine patterning. Also, it becomes difficult to exert satisfactory characteristics in 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 Document 3). However, this urethane compound has no reactivity to active energy rays. For this reason, it is necessary to use other reactive compounds together in order to obtain reactivity to active energy rays, that is, in order to obtain a resin composition that can be finely patterned by photolithography. It has not been possible to exhibit flexibility, heat resistance, etc. at a high level.
Further, Patent Document 4 discloses a reactive polyurethane compound imparted with a reactivity to an active energy ray, but the performance is unsatisfactory in terms of flexibility for bending at 180° C. which is actually used in a flexible printed circuit board. Was enough.

JP-A-9-52925 JP, 2003-147043, A JP 2006-124681 A JP, 2011-140624, A

In the present invention, while being capable of optical patterning, heat resistance that can withstand heat such as solder at the time of manufacturing a substrate and heat generation of an element used for the substrate, reliability of maintaining high insulation for a long time, plating treatment, etc. It is an object to provide a material having flexibility and toughness required for a flexible substrate etc. without impairing the basic characteristics required for a solder resist etc. such as chemical resistance to chemical treatment.

In order to solve the above problems, the inventors of the present invention have conducted extensive studies, and as a result, polyurethane compounds obtained by using an ester diol compound with a dicarboxylic acid having a specific structure, its acid-modified compounds and those The inventors have found that a resin composition containing the above-mentioned material can solve the above-mentioned problems, and have completed the present invention. That is, the present invention is

[1] Obtained by reacting an epoxy compound (a) having two epoxy groups in one molecule with a compound (b) having at least one ethylenically unsaturated group and one carboxyl group in one molecule. Unsaturated epoxycarboxylate compound (c), compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, polyester diol compound (e) with dicarboxylic acid having 10 or more carbon atoms and one molecule A polyurethane compound (A) obtained by reacting with a compound (f) having two isocyanate groups,
[2] The polyurethane compound (A) according to the above item [1], which comprises a sebacic acid polyester diol or a dimer acid polyester diol as the polyester diol compound (e).
[3] An acid-modified polyurethane compound (B) obtained by reacting the polyurethane compound (A) with a polybasic acid anhydride (g),
[4] An active energy ray-curable resin composition containing the polyurethane compound (A) described in [1] or [2] above and/or the acid-modified polyurethane compound (B) described in [3] above.
[5] 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),
[6] The active energy ray-curable resin composition according to the above [4] or [5], which is a forming material,
[7] The active energy ray-curable resin composition according to the above [6], which is a film-forming material,
[8] The active energy ray-curable resin composition according to any one of the above items [4] to [7], which is a resist material.
[9] A cured product of the active energy ray-curable resin composition according to any one of [4] to [8] above.
[10] An article overcoated with the cured product according to the above item [9],
Regarding

The polyurethane compound (A) of the present invention uses a polyester diol compound with a dicarboxylic acid having 10 or more carbon atoms, and since flexibility can be improved by incorporating a long-chain alkyl, the acid-modified polyurethane compound (B ), an active energy ray-solidifying type resin composition containing them and a cured product thereof have heat resistance capable of withstanding heat of solder or the like at the time of manufacturing a substrate and heat generated by an element used for the substrate, while being capable of photo-patterning, and long-term. The flexibility required for flexible substrates, etc., without compromising the basic characteristics required for solder resists, color resists, etc. such as reliability of maintaining high insulation property over a long time, chemical resistance to chemical treatment such as plating treatment, etc. It is possible to provide a material having toughness, and it can be particularly suitably used as a film forming material that is required to have flexibility, such as a solder resist for a flexible substrate.

Hereinafter, the present invention will be described in detail.
The polyurethane compound (A) of the present invention is a compound (b) having at least one ethylenically unsaturated group and one carboxyl group in one molecule in addition to the epoxy compound (a) having two epoxy groups in one molecule. ), an unsaturated epoxycarboxylate compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a polyester diol compound with a dicarboxylic acid having 10 or more carbon atoms. It is obtained by reacting (e) with a compound (f) having two isocyanate groups in one molecule.

That is, the polyurethane compound (A) of the present invention is produced by two reaction steps. First, an unsaturated epoxy compound is prepared by reacting an epoxy compound (a) having two epoxy groups in one molecule with a compound (b) having at least one ethylenically unsaturated group and one carboxyl group in one molecule. In this step, the carboxylate compound (c) is obtained. In the present invention, this step is referred to as a carboxylation step.
Then, the unsaturated epoxycarboxylate compound (c) thus obtained, the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and the polyester diol compound (C) having a carbon number of 10 or more (dicarboxylic acid) e) and the step of reacting the compound (f) having two isocyanate groups in one molecule. In the present invention, this step is referred to as a urethanization step.

The unsaturated epoxycarboxylate compound (c) 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 (a) in one molecule. It is a compound.

In the subsequent urethanization step, two hydroxyl groups of the unsaturated epoxycarboxylate compound (c), two hydroxyl groups of the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a carbon number of 10 The polyurethane compound (A) is obtained by reacting the two hydroxyl groups of the polyester diol compound (e) with the above dicarboxylic acid with the compound (f) having two isocyanate groups in one molecule.

First, the carboxylation step will be described in detail.
One molecule of the epoxy compound (a) having two epoxy groups in one molecule (hereinafter, also simply referred to as “epoxy compound (a)”) used for producing the polyurethane compound (A) of the present invention is one molecule. There is no particular limitation as long as it has two epoxy groups. With a monofunctional epoxy compound, the molecular weight of the polyurethane compound (A) obtained by the urethanization step cannot be adjusted, and with a trifunctional or higher functional epoxy compound, a multi-branched structure is obtained, so that suitable physical properties of the cured product can be obtained. Is difficult.

Examples of the epoxy compound (a) include bisphenol diglycidyl ethers, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol diglycidyl ethers such as bisphenol full orange glycidyl ether, biphenol diglycidyl ether, and tetramethyl. Aromatic diglycidyl ether compounds such as biphenyl glycidyl ethers such as biphenol glycidyl ether; alkyldiol diglycidyl ethers such as hexanediol diglycidyl ether, alkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether, cyclohexanediol Saturated hydrocarbon diglycidyl ether compounds such as cycloalkyl diol diglycidyl ethers such as diglycidyl ether and hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate Examples include so-called bifunctional alicyclic epoxy compounds such as (Celoxide 2021 manufactured by Daicel Chemical Co., Ltd.) and 1,2,8,9-diepoxylimonene (Celoxide 3000 manufactured by Daicel Chemical Co., Ltd.).

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

Further, the epoxy compound (a) is preferably one having no hydroxyl group. This is because the unsaturated epoxycarboxylate compound (c) obtained in the epoxycarboxylation step becomes a trifunctional or higher functional polyol compound, which makes it difficult to control the molecular weight of the polyurethane compound (A).

A compound (b) having at least one ethylenically unsaturated group and one carboxyl group in one molecule used in the production of the polyurethane compound (A) of the present invention (hereinafter, also simply referred to as “compound (b)”). ) Has the purpose of introducing an ethylenically unsaturated group into the reactive polyurethane compound (A) and converting the epoxy compound (a) into a diol compound capable of reacting with an isocyanate group. The number of ethylenically unsaturated groups in the compound (b) is preferably 1 to 4.

Examples of the compound (b) include (meth)acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or unsaturated divalent saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives. A reaction product with a group-containing monoglycidyl compound can be 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, Half-esters, saturated or unsaturated, which are equimolar reaction products of a (meth)acrylic acid dimer, a saturated or unsaturated dibasic acid anhydride, and a (meth)acrylate derivative having one hydroxyl group in one molecule. Examples thereof include half-esters which are equimolar reaction products of a dibasic acid and monoglycidyl (meth)acrylate derivatives.

Among 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 used as an active energy ray-curable resin composition.

Further, the compound (b) is preferably one having no hydroxyl group in the compound.

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

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

When a solvent is used, the amount used should be appropriately adjusted depending on the viscosity and purpose of the resin to be obtained, but the solid content is preferably 99 to 30% by weight, more preferably 99 to 45% by weight. It may be used as follows. When the compound used in the reaction has a high viscosity, the viscosity is suppressed and the reaction proceeds properly.

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 that is a mixture thereof, white gasoline, Solvent naphtha and the like can be mentioned. Further, an ester solvent, an ether solvent or a ketone solvent 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 mono. Acetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate and other mono or polyalkylene glycol monoalkyl ether monoacetates, glutaric acid glutaric acid etc. Examples thereof include dialkyl succinates such as acid dialkyl and dimethyl succinate, and polycarboxylic acid dialkyl esters such as dialkyl adipate such as dimethyl adipate.

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, 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, the reactive compound (C) described below may be used alone or in combination as a solvent. In this case, the curable resin composition can be used as it is.

In the carboxylation step, it is preferable to use a catalyst 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 (a), the compound (b), and the solvent when the solvent is used. It is a degree. At that time, the reaction temperature is 60 to 150° C., and the reaction time is preferably 5 to 60 hours.
Examples of the catalyst include common basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate. Etc.

Further, a thermal polymerization inhibitor may be used, and 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 or the like.

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

Next, the urethanization step will be described in detail.
The compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule (hereinafter, also simply referred to as "compound (d)") used in the production of the polyurethane compound (A) of the present invention is A carboxyl group is introduced into the polyurethane compound (A) to make it soluble in an alkaline aqueous solution necessary for photopatterning. The number of carboxyl groups in the compound (d) is preferably 1 to 4.

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

By using the polyester diol compound (e) with a dicarboxylic acid having 10 or more carbon atoms (hereinafter, also simply referred to as “polyester diol compound (e)”) for producing the polyurethane compound (A) of the present invention, sensitivity and heat resistance can be improved. It is possible to combine properties, chemical resistance and flexibility with a high level. The upper limit of the carbon number is preferably 100 or less.
The polyester diol compound (e) 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 (e) include diol dicarboxylic acid ester diols in which a diol compound and a dicarboxylic acid are connected by an ester bond. The diol compound is not particularly limited as long as it is a compound having two hydroxyl groups other than the unsaturated epoxycarboxylate compound (c) and the compound (d).

Examples of the 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 sebacic acid polyester diol, propylene glycol sebacic acid polyester diol, butylene glycol sebacic acid polyester diol, neopentyl glycol sebacic acid polyester. Diol, methylpentanediol sebacic acid polyester diol, hexanediol sebacic acid polyester diol, ethylene glycol sebacic acid polyester diol, ethylene glycol dimer acid polyester diol, propylene glycol dimer acid polyester diol, hexanediol dodecane diacid ester diol, ethylene glycol dodecane Examples thereof include diacid ester diol and ethylene glycol addecane diacid ester diol.

Of these, polyester diol compounds (e) are particularly preferably sebacic acid polyester diols and dimer acid polyester diols because they exhibit suitable flexibility.

The above-mentioned polyester diol sebacate is a reaction product obtained by reacting sebacic acid with a diol, and the polyester diol dimer acid is a reaction product obtained by reacting a dimer acid with a diol.

The above-mentioned dimer acid is a dibasic acid, in which two monobasic fatty chains (usually having 18 carbon atoms) are double-bonded by a carbon-carbon covalent bond so that the molecular weight obtained is double. A basic acid. A typical compound thereof is a dimer obtained by polymerizing an unsaturated fatty acid such as linoleic acid, oleic acid, elaidic acid, tall oil and fatty acid. Generally, since the unsaturated fatty acid having 18 carbon atoms is used as a raw material, the main component is a dicarboxylic acid having 36 carbon atoms.

Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4- Trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol and the like can be mentioned.

The polyester diol compound (e) preferably has a molecular weight of 250 to 5,000, more preferably 650 to 3,000. When the molecular weight is smaller than this range, the effect of imparting flexibility is low, and when the molecular weight is larger than this range, the heat resistance is greatly reduced.

The compound (f) having two isocyanate groups in one molecule (hereinafter, also simply referred to as “isocyanate compound (f)”) used for producing the polyurethane compound (A) of the present invention is an unsaturated epoxycarboxy. It is used in the urethanization step of the rate compound (c), the compound (d) and the hydroxyl group of the polyester diol compound (e), and imparts suitable flexibility to the polyurethane compound (A).

Examples of the compound (f) 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 alicyclic diisocyanates include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylenebisphenylene diisocyanate, and the like.

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

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

In the urethanization step, an unsaturated epoxy carboxylate compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a polyester diol compound with a dicarboxylic acid having 10 to 100 carbon atoms The mixture of (e) and the compound (f) having an isocyanate group are mixed.

In the production of the polyurethane compound (A), (the number of moles of the unsaturated epoxycarboxylate compound (c)+the number of moles of the compound (d)+the number of moles of the polyester diol compound (e))/(the mole of the isocyanate compound (f)) (Number), 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 storage stability of the polyurethane compound (A), the polyurethane compound (A) is charged so that the number of hydroxyl groups is at least larger than that of the isocyanate groups in the urethanization step so that the isocyanate groups do not finally remain.
Further, if it is larger than this range, the molecular weight of the obtained polyurethane compound (A) tends to be too small, and it tends to be difficult to obtain a toughened cured product. If it is too small, the molecular weight of the obtained polyurethane compound (A) becomes large. If it is too much, the developability may be adversely affected.

In the production of the polyurethane compound (A) of the present invention, preferable weights of the unsaturated epoxycarboxylate compound (c), the compound (d), the polyester diol compound (e) and the isocyanate compound (f). The ratio is 5 to 65 parts by weight of the unsaturated epoxycarboxylate compound (c), 5 to 25 parts by weight of the compound (d), and 0 of the polyester diol compound (e) when the total weight of the resin composition is 100 parts. 0.5 to 60 parts by weight, and the isocyanate compound (f) is 20 to 40 parts by weight. Within this range, a polyurethane compound (A) having photopatterning properties and developability with an alkaline aqueous solution and having suitable properties as a resist material can be obtained, and high heat resistance, chemical resistance, and outstanding flexibility are particularly high. It is possible to obtain a cured product having a good dimensional balance.

In the urethanization step, the reaction can be carried out with or without a solvent. When a solvent is used, it is not particularly limited as long as it is an inert solvent for the urethanization reaction.

When a solvent is used, its amount should be appropriately adjusted depending on the viscosity and purpose of the resin to be obtained, but the solid content is preferably 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.

Examples of the solvent include the same solvents as those exemplified in the carboxylation step. If the reaction is inert, the reactive compound (C) described below may be used alone or as a mixture as a solvent. In this case, the curable composition can be used as it is.

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 a catalyst, but a catalyst can be used to accelerate the reaction. When a catalyst is used, its amount is about 0.01 to 1% by weight based on the total amount of the reactants. Examples of the catalyst include a general basic catalyst, for example, a Lewis base catalyst such as tin ethylhexanoate.

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

The reaction in the urethanization step is terminated by the fact that almost no isocyanate group remains. The end point of the reaction is determined by an infrared absorption spectrum measurement method by observing a peak near 2250 cm ⁻¹ derived from an isocyanate group or by a titration method described in JIS K1556:1968.

The preferred molecular weight range of the polyurethane compound (A) of the present invention thus obtained is in the range of 1,000 to 30,000 in terms of polystyrene-reduced weight average molecular weight in GPC, and more preferably in the range of 3,000 to 20,000. If the molecular weight is smaller than this, the toughness of the cured product may not be sufficiently exhibited, and if it is larger than this, not only the viscosity becomes high and coating becomes difficult, but also the developability decreases. 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 (g), if necessary. As a result, the acid value required for alkali development can be appropriately added not only in the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, but also in accordance with the required resin properties. 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 (g) is reacted with the hydroxyl group remaining after the urethanization reaction to introduce a carboxyl group via an ester bond. Therefore, it is impossible to acid-add more than the equivalent amount of the hydroxyl group remaining after the urethanization step.

Examples of the polybasic acid anhydride (g) include compounds having a cyclic acid anhydride structure in one molecule, and succinic anhydride (SA) from the viewpoint of developability of alkaline aqueous solution, 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.

The acid addition step is performed by adding the polybasic acid anhydride (g) to the polyurethane compound (A). The amount of the polybasic acid anhydride (g) used is required for the set value of the polyurethane compound (A), that is, the acid value derived from the compound (d), the amount of residual hydroxyl groups, and the polyurethane compound (A). It may be appropriately changed based on the acid value.

When the polyurethane compound (A) and/or the acid-modified polyurethane compound (B) of the present invention is used as an alkali developing resist, the solid content acid value (JIS K5602-1-2-1:1999) of the finally obtained polyurethane compound. It is preferable to set 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 aqueous alkaline solution. That is, it is possible to exert a good balance between the good solubility of the active energy ray non-irradiated portion and the good solubility of the active energy ray irradiated portion.

In the acid addition step, it is preferable to use a catalyst for promoting the reaction, and the amount thereof is about 0.1 to 10% by weight based on the total amount of the reaction product. At that time, 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 octanoate, zirconium octanoate and the like.

In the acid addition step, the reaction can be carried out with or without 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. In the case where a solvent is used in the urethanization step, which is the previous step, the acid addition reaction may be carried out without removing the solvent if both reactions are inert.

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

If the reaction is inert, the reactive compound (C) described below may be used alone or as a mixture as a solvent. In this case, the curable composition can be used as it is.

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.

While appropriately sampling the reaction in the acid addition step, the end point is set when the acid value of the reaction product is within a 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). Further, a resin composition containing a reactive compound (C) other than the components (A) and (B) is preferable.

Examples of the reactive compound (C) include radical reaction type acrylates, cation reaction type epoxy compounds, and vinyl compounds sensitive to both of them.

Examples of radical-reactive 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, polyethylene glycol (meth)acrylate. Examples thereof include monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like.

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. (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 di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol hydroxybivalate, reaction product of dipentaerythritol and ε-caprolactone Poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide addition , Pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, and the like.

The cation-reactive epoxy compound is not particularly limited as long as it is a compound having an epoxy group including the epoxy compound (a), and examples thereof include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, and butyl glycidyl ether. , Bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Cyracure UVR-6110" manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4 -Epoxy cyclohexane carboxylate, vinyl cyclohexene dioxide ("ELR-4206" manufactured by Union Carbide Co., Ltd.), limonene dioxide ("Celoxide 3000" manufactured by Daicel Chemical Industries, Ltd.), allyl cyclohexene 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( Union Carbide "Cyracure UVR-6128"), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl)diethyl siloxane etc. are mentioned.

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, methylstyrene, ethylstyrene and the like.
Examples of other vinyl compounds include triallyl isocyanurate and trimetallyl 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 other than the polyurethane compound (A) and the 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 having a functional group sensitive to active energy rays derived from an epoxy compound in the same molecule, and these bonds You may use the oligomer etc. which are used compositely.

Of these, radical-curable acrylates are preferable as the reactive compound (C). In the case of the cation-reactive type, a carboxylic acid and an epoxy group react with each other, so that it is necessary to use a two-liquid mixed type for preparation when used.

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

The active energy ray-curable resin composition of the present invention contains the polyurethane compound (A) and/or the acid addition polyurethane compound (B) in the composition in an amount of 97 to 5% by weight, preferably 87 to 10% by weight. The reactive compound (C) other than (A) and the 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 uses, other components may be contained in an upper limit of about 75% by weight, if 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 and the like.

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-hydroxycyclohexylphenylketone, 2-methyl-1-[4-( Acetophenones such as methylthio)phenyl]-2-morpholino-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethyl Thioxanthones such as thioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone And the like; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

As the cationic photopolymerization initiator, a diazonium salt of Lewis acid, an iodonium salt of Lewis acid, a sulfonium salt of Lewis acid, a phosphonium salt of Lewis acid, other halides, triazine initiators, borate initiators, and others A photo-acid generator etc. are mentioned.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L/SI-80L/SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. 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 (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 and the like.

Examples of other halides include 2,2,2-trichloro-[1-4′-(dimethylethyl)phenyl]ethanone (Trigonal PI manufactured by AKZO, etc.) and 2,2-dichloro-1-(4- Examples include phenoxyphenyl)ethanone (Sandray 1000 and the like manufactured by Sandoz), α,α,α-tribromomethylphenyl sulfone (BMPS and the like manufactured by Iron and Steel Chemical Co., Ltd.), and the like.
Examples of the triazine-based initiator include 2,4,6-tris(trichloromethyl)triazine and 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)triazine (Triazine A manufactured by Panchim Co., Ltd.). , 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 and the like), 2,4-bis(trichloromethyl)-6-(4′-methoxynaphthyl)triazine (Trichimine B and the like manufactured by Panchim Co.), 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 (Sanwa Chemical) Manufactured by the company) and the like.

Examples of the baud rate initiator include NK-3876, NK-3881 and the like (all manufactured by Nippon Senso Dye).
Examples of other photoacid generators and the like include 9-phenylacridine, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2-biimidazole (black Kinkasei Co., Ltd., such as biimidazole), 2,2-azobis(2-amino-propane)dihydrochloride (Wako Pure Chemical Industries, Ltd., V50, etc.), 2,2-azobis[2-(imidazolin-2yl)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 manufactured by Ciba Geigy), bis(eta-5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium (Ciba Geigy) CGI-784 etc. manufactured by the company).

Furthermore, an azo-based initiator such as azobisisobutyronitrile and a peroxide-based radical-type initiator such as benzoyl peroxide which are sensitive to heat may be used together. Further, both radical-type and cation-type initiators may be used in combination, and one of the initiators may be used alone or two or more of them may be used in combination.

Of these, radical type photopolymerization initiators are particularly preferable in view of the characteristics of the polyurethane compound (A) of the present invention.

Further, the active energy ray-curable resin composition of the present invention may contain a curing agent depending on the intended use. The curing agent is used in order to obtain a strong cured film by reacting with an acidic group contained therein, 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 having two or more epoxy groups in one molecule is preferable. This is because it is possible to obtain a stronger cured product 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 is likely to be brittle, and when it is larger than this, the cured product is likely 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 required properties, and known general epoxy compounds 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 phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type. Examples thereof include epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac 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 (manufactured by Dow Chemical Co., Ltd.), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.
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.), and UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.), and the like.

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

Examples of the bisphenol type epoxy resin include jER828, jER1001 (all manufactured by Japan Epoxy Resins Co., Ltd.), UVR-6410 (manufactured by Union Carbide Co.), D.I. E. R-331 (manufactured by Dow Chemical Co.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.), and other bisphenol-A type epoxy resins, 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 (all manufactured by Nippon Kayaku Co., Ltd.) 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 KK), YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by DIC Co., Ltd.) and jER E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Co., Ltd.).
Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
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.) and the like.

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

When the epoxy compound is contained, a suitable blending amount thereof 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. If the blending amount is less than this amount, the obtained cured product tends to be soft, and if it is too large, the curability and the like may be adversely affected due to the problem of balance with the epoxy curing agent described below.

Other additives that may be contained in the active energy ray-curable resin composition of the present invention include, for example, a thermosetting catalyst such as melamine, a thixotropy imparting agent such as Aerosil, a silicone-based or fluorine-based leveling agent, and the like. Examples thereof include antifoaming 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 preferably used in combination with a flame retardant. As the preferred flame retardant, known general ones can be used, and halogenated flame retardants such as brominated epoxy resin and bromodiphenyl ether, phosphazene resins, phosphoric ester resins such as 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 a coloring pigment intended for coloring and an extender pigment not intended for coloring.
Examples of the color pigment include phthalocyanine-based, azo-based, quinacridone-based organic pigments, carbon black, and inorganic pigments such as titanium oxide.
Examples of the extender pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

Further, it may contain resins (so-called inert polymers) that do not show reactivity with active energy rays. Examples of the resins include epoxy resins other than 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 a solder resist application, it is preferable to use an epoxy resin in combination. By further carboxylating the carboxyl groups remaining after curing with active energy rays, a strong cross-linked structure is formed, and the cured product has excellent water resistance and hydrolyzability.

The volatile solvent that 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 a range of up to %.

The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. 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 rays. Among these, ultraviolet light, laser light, visible light, or electron beam is preferable in consideration of the preferred use of the present invention.

The present invention also 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, clear coat, adhesives and adhesives for laminating and optical disks. Such materials include adhesive materials such as agents, solder resists, etching resists, resist materials such as micromachine resists, and the like.
Further, a so-called dry film is also a film-forming material, in which a film-forming material is temporarily applied to a releasable substrate to form a film, which is then attached to an originally intended substrate to form a film. ..

The present invention also includes the use of the active energy ray-curable resin composition as a film-forming material for electrical insulation. That is, a material required to have electrical insulation such as a solder resist material for circuit boards, an insulating molding material, an interlayer insulating material, a semiconductor protective film material, and a wiring coating material corresponds to this.

In the present invention, a film layer of the composition is formed on a substrate, and then, active energy rays such as ultraviolet rays are partially irradiated, and drawing is performed by utilizing the difference in physical properties between the irradiated portion and the non-irradiated portion. Use of the active energy ray-curable resin composition as an active energy ray-sensitive resist material to be intended is also included. That is, the irradiated portion or the unirradiated portion is removed by some method, for example, by dissolving with a solvent or an alkaline solution, and used for the purpose of drawing.

The present invention also includes the active energy ray-curable resin composition used for the permanent resist. Permanent resist is not used on the premise that it will be peeled off after drawing, out of the above resist materials, and it will continue to maintain its purpose and function without peeling off until it is actually used as the base material It is a thing.

The active energy ray-curable resin composition for resist of the present invention can be applied to various materials that require patterning, and among them, it is particularly useful as a solder resist material or an interlayer insulating material for a build-up method, and further, an optical waveguide. It can also be used as a printed wiring board, an optoelectronic substrate, or an electric/electronic/optical substrate such as an optical substrate.

Particularly suitable applications are photosensitive films, photosensitive films with a support, insulating resin sheets such as prepregs, circuit boards (used for laminated boards, multilayer printed wiring) by taking advantage of the characteristics of good heat resistance and developability. (Plate application etc.), solder resist, underfill material, die bonding material, semiconductor encapsulating material, hole filling resin, component embedding resin, etc., and can be used in a wide range of applications where a resin composition is required. Among them, a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a cured product of a photosensitive resin composition) Is used as an interlayer insulating layer) and a resin composition for forming a plating (a multilayer printed wiring board having a cured product of a photosensitive resin composition having a plating formed thereon).

Further, it can exhibit good developability even at a high pigment concentration, and can be suitably used for color resists, resist materials for color filters, especially black matrix materials.

Further, by utilizing the characteristic of being able to obtain a cured product that is flexible yet tough, it is possible to maximize the effects of the present invention when used for an insulating material application for a flexible substrate that requires flexibility, It is a suitable application.

The method for forming the film is not particularly limited, intaglio printing method such as gravure, relief printing method such as flexo, stencil printing method such as silk screen, lithographic printing method such as offset, roll coater, knife coater, die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

The present invention also includes a cured product obtained by irradiating the active energy ray-curable resin composition with an active energy ray to cure the resin composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, in the examples, "parts" means "parts by weight" unless otherwise specified.

The softening point and the 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 unsaturated epoxycarboxylate compound (c) (carboxylation step)
1840 g of bisphenol A type epoxy resin (RE-310S, WPE=184 g/eq, manufactured by Nippon Kayaku Co., Ltd.) as the epoxy compound (a), and acrylic acid (abbreviation AA, Mw=72) as the compound (b). 720 g, triphenylphosphine 30 g as a catalyst, and propylene glycol monomethyl ether monoacetate (abbreviation PGMAc) as a solvent so that the solid content ratio becomes 80%, and the reaction is carried out at 100° C. for 24 hours to obtain an unsaturated epoxycarboxylate compound ( c) A solution was obtained.

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. Further, the epoxy value was measured to be 13000 g/eq, and it was also confirmed that the epoxy group was sufficiently reacted.

(Example 1): Preparation of polyurethane compound (A) (urethane forming step)
The amount of the unsaturated epoxycarboxylate compound (c) solution obtained in Synthesis Example 1 in the reaction tank is described in Table 1 (the described value is the solid content conversion value), and dimethylolpropionic acid as the compound (d) is described in Table 1. The amount of polyester diol listed in Table 1 as the polyester diol compound (e), the amount of solid content of 50% as the polyurethane compound (A) using propylene glycol monomethyl ether acetate (abbreviation PGMAc) as the solvent Thus, 47.5 g was added and dissolved with stirring.
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. After that, hexamethylene diisocyanate as the isocyanate compound (f) in the amount shown in Table 1 was added and reacted using a dropping funnel. After completion of dropping, the reaction was continued for 10 hours, and it was confirmed by infrared absorption spectrum that there was no absorption peak derived from an isocyanate group, and thus a polyurethane compound (A) was obtained.

(Comparative Example 1): Preparation of comparative polyurethane compound Using the carboxylate compound (c) prepared in Synthesis Example 1, the polyurethane compounds in Table 1 were prepared in the same manner as in Example 1.

[Table 1]

Abbreviations in the table:
(C+d+e)/f: Ratio of the total number of moles of hydroxyl groups contained in the reaction system and the total number of moles of isocyanate URIC SE-2013C: Sebacic acid polyester polyol (Ito Oil Co., Ltd.) average molecular weight 2000
URIC-3091U: Sebacic acid polyester polyol (manufactured by Ito Oil Co., Ltd.) average molecular weight 1000
PRIPLAST XL 101: dimer acid polyester polyol (manufactured by CRODA Co.) average molecular weight 2200
PCDLT-6001: Polycarbonate diol (manufactured by Asahi Kasei Corporation) Average molecular weight 1000

(Example 2): Preparation of acid-modified polyurethane compound (B) (acid addition step)
In the reaction tank, the PGMAc solution of the polyurethane compound (A) obtained in Example 1 was used in the amount shown in Table 2, and the acid anhydride shown in Table 2 was used as the polybasic acid anhydride (g) in Table 2. The indicated amount (calculated value as solid content acid value of 90 mg·KOH/g) was added. Further, PGMAc was added as a solvent so that the final solid content was 50%, that is, the same weight as the acid anhydride. 0.2 g of triethylamine was added as a catalyst and stirred to dissolve.

After dissolution, the mixture was heated to 100° C. with stirring and reacted for 50 hours to obtain an acid-modified polyurethane compound (B). After the reaction was completed, the acid value was measured to confirm the completion of the reaction.

(Comparative Example 2): Preparation of comparative acid-modified polyurethane compound Using the polyurethane compound prepared in Comparative Example 1, a urethane-forming step was carried out in the same manner as in Example 2 to prepare an acid-modified urethane compound. ..

[Table 2]

Abbreviations in the table:
AV: solid content acid value (mg·KOH/g): The measurement was performed as a solution and converted into a value in solid content.
Mw: Weight average molecular weight measured using gel permeation chromatograph (polystyrene standard conversion value)
SA: succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd.)

(Example 3): Preparation and evaluation of solder resist material composition for flexible substrate 6.0 g of the acid-modified polyurethane compound (B) obtained in Example 2, DPCA-20 (commercial product) as a reactive compound (C) Name: Nippon Kayaku Co., Ltd. 1.2 g, Irgacure 907 (Ciba Specialty Chemicals) 0.27 g and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) as photopolymerization initiators. The solid content concentration was adjusted to 60% by adding 01 g, 0.01 g of TPP as a thermosetting catalyst and diethylene glycol monomethyl ether monoacetate as a concentration adjusting solvent. Then, it was uniformly dispersed to obtain a resist material resin composition.

Each of the evaluation items will be described in detail.

Crumpling resistance evaluation (abbreviation in the table: flexibility)
A bisphenol A type epoxy resin (trade name: YD-134, manufactured by Nippon Steel & Sumitomo Metal Corporation) was added to the resist material composition as a curing component so as to be 120% with respect to the carboxy group. The obtained composition was applied to a polyimide film Kapton 100H (manufactured by DuPont Toray) so as to have a thickness of 20 μm with an applicator, and the coating film was dried by a hot air dryer at 80° C. for 60 minutes.
Then, using an ultraviolet irradiator (CS 30L-1 manufactured by GS YUASA), ultraviolet rays were irradiated at an energy of 500 mJ/cm ² . Then it was cured in an oven at 150° C. for 30 minutes.
The cured film was subjected to a 180 degree fold test and evaluated by the number of times until the cured film was cracked.

Developability evaluation (abbreviation in the table: Developability)
With respect to the developability, the coating film before ultraviolet irradiation was subjected to spray development using a 1% sodium carbonate aqueous solution as a developing solution. The developability was evaluated by the so-called break time, which is the time until the coating film is completely dissolved (unit: second).
× ・・Swelling and peeling

Solder heat resistance evaluation (abbreviation in the table: heat resistance)
The test was conducted in accordance with JIS C-5016 10.3:1994. A pattern film having a cured resist film formed thereon was repeatedly immersed in a heated solder bath three times. After the dipping, the degree of peeling of the flexible substrate was evaluated by using a base peel test.
Solder bath temperature: 260℃
Immersion time for one time: 60 seconds Evaluation criteria: The number of front substrate (100) was used as a denominator, and the number of remaining squares was used as a numerator.

[Table 3]

From the above results, the active energy ray-curable resin composition using the acid-modified polyurethane compound (B) of the present invention impairs the basic characteristics of solder resist and the like such as heat resistance of solder and developability. It was found that it is possible to obtain a cured film having good resistance to folding.
In view of this characteristic, it is clear that the active energy ray-curable resin composition containing the acid-modified polyurethane compound (B) of the present invention can be particularly suitably used as a solder resist for flexible substrates.

The polyurethane compound (A), the composition containing the same and the cured product thereof of the present invention are materials having flexibility, and are suitable as resist materials for flexible substrates, color resists for flexible displays, spacer resists and the like. It can be used.

Claims (7)

Unsaturated epoxy obtained by reacting an epoxy compound (a) having two epoxy groups in one molecule with a compound (b) having at least one ethylenically unsaturated group and one carboxyl group in one molecule Carboxylate compound (c), compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, polyester diol compound (e) with dicarboxylic acid having 10 or more carbon atoms, and two in one molecule A polyurethane compound (A) obtained by reacting the compound (f) having an isocyanate group as described above, wherein the polyester diol compound (e) contains a sebacic acid polyester diol or a dimer acid polyester diol. An acid-modified polyurethane compound (B) obtained by reacting the polyurethane compound (A) according to claim 1 with a polybasic acid anhydride (g). Polyurethane compound according to claim 1 (A), or acid-modified polyurethane compound according to claim 2 (B), the active energy ray curable resin composition comprising a. The active energy ray-curable resin composition according to claim 3, further comprising a reactive compound (C) other than the polyurethane compound (A) and the acid-modified polyurethane compound (B). The active energy ray-curable resin composition according to claim 3, which is a resist material. A cured product of the active energy ray-curable resin composition according to any one of claims 3 to 5 . An article overcoated with the cured product according to claim 6 .