JPH11228688A - Alkali-soluble curable resin, its production, curable resin composition and its formed film material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin capable of exhibiting excellent photosensitivity, aqueous alkali developing properties and toughness, adhesivity, heat resistance, etc., after curing, useful as a liquid resist material, etc., by making an unsaturated double bond and a carboxyl pendant from the OH of a phenoxy resin. SOLUTION: This alkali-soluble curable resin is shown by the formula [Ar<1> and Ar<2> are each H, a halogen or a dihydric aromatic phenol residue containing an (ether bond-containing) 1-12C hydrocarbon group as a substituent group; Ar<3> is Ar<1> or Ar<2> ; R is H or methyl; R' is a 2-20C aliphatic, alicyclic or (substituted) aromatic polyfunctional carboxylic acid residue; (x) is 0 or 1; (y) is 1 or 2; (p), (q) and (r) are each a mol fraction of each structural unit and are 0.3-0.6, 0.4-0.7 and 0-0.3, respectively and p+q+r=1] and is obtained, for example, by reacting a side chain OH in a corresponding phenoxy resin with a fixed amount of an α,β-unsaturated monoisocyanate and then a polyfunctional carboxylic acid anhydride in this order.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous alkali-soluble curable resin, and more particularly to a photosensitive resin excellent in mechanical toughness, heat resistance, adhesion to metal and the like. In particular,
Useful as printed wiring board manufacturing, metal precision processing, etching of glass and stone, plastic relief material, material for printed printing board.Especially, selectively exposed to actinic light through a negative film and developing unexposed parts In the formation of a solder resist pattern by using, the exposed part is excellent in photosensitivity and the aqueous alkali development of the unexposed part is possible, and the exposed part is excellent in mechanical toughness, solvent resistance, electrical insulation, solder heat resistance, etc. The present invention relates to a photosensitive curable resin having a resist forming ability, a production method, a curable resin composition, and a film molded product thereof.

[0002]

2. Description of the Related Art In recent years, with the rapid development of multimedia, the degree of reduction in the size and weight of components mounted on equipment has been increasingly increasing. In particular, in the field of integrated circuit components, as the degree of integration and performance of devices increases, the mounted chip becomes larger and more pins, while the package becomes smaller and thinner to increase the mounting density. . For this reason, the thickness of the sealing resin layer has been significantly reduced, and the mounting method has shifted from the conventional pin insertion type to the surface mounting type that can be mounted on both sides of the printed circuit board, and a batch bonding method using solder reflow It is easy to receive a strong thermal shock. At present, COBs, MCMs, build-ups, stack vias, printed circuit boards with built-in thin film devices, circuit boards with embedded layers, and the like are being developed one after another as mounting methods. In such industrial fields, curable resins, particularly unsaturated polyester resins, vinyl ester resins, various oligomer acrylates, diallyl phthalate, prepolymers and the like are known as resins that are cured by radical polymerization reactions,
in use. For example, JP-A-03-3297, JP-A-06-90087, and JP-A-06-224529
And JP-A-07-170070, all of which use a polyepoxy resin having a relatively low molecular weight such as a cresol novolak type epoxy resin as the epoxy acrylate, and use α, β such as acrylic acid. -When using a product obtained by reacting an unsaturated carboxylic acid, bleeding during printing, bleeding, unavoidable that there are defects such as sagging, and the cured product is also poor in toughness,
Poor thermal shock resistance when performing multi-layering. With the diversification of new applications and the sophistication of functions, there is a current situation where existing resins cannot sufficiently cope with such problems.

[0003]

For this reason, attempts have been made to overcome the conventional disadvantages caused by increasing the molecular weight of the resin component. For example, an addition reaction product of glycidyl methacrylate to a hydroxyl group in a phenoxy resin (Tanaka) Tanaka et al., Proceedings of the 47th Annual Meeting of the Chemical Society of Japan, I, 3T, pp. 46, 198.
3), a composition comprising a reaction product of a carboxyl group-containing methacrylic copolymer and glycidyl methacrylate and a crosslinkable monomer (JP-A-06-26070), an addition reaction between a hydroxyl group in a phenoxy resin and isocyanateethyl methacrylate Product (JP-A-61-296353)
JP-A-63-75023 and JP-A-63-8142.
No. 2, Japanese Patent Publication No. 05-69125). However, all of these prior arts are of the solvent development type. Further, in the resin laminating method, in addition to forming a film by evaporating a solvent from a liquid resin containing a solvent, a film formed into a dry film in advance has been required and studied. For example, JP-A-57-55914 describes the method. Although the gazette discloses a resin composition containing urethane di (meth) acrylate and a linear polymer having a specific glass transition temperature, it has sufficient toughness as a dry film, solder heat resistance, adhesion and the like. Not. As described above, at present, a material that can be developed with an aqueous alkali in an unexposed portion, has excellent resist suitability in an exposed portion, can cope with various circuit forming methods, and particularly can be used as a dry film is still found. Absent.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies on resins suitable for new uses. As a result, a specific ratio of α, β-unsaturated monoisocyanate and polyamine to hydroxyl groups in a phenoxy resin was determined. The resin obtained by reacting a polycarboxylic anhydride can achieve both excellent photosensitivity and aqueous alkali developability, and furthermore, the mechanical toughness of the cured product, adhesion to metal, heat resistance, solvent resistance, and electric resistance. The present inventors have found a resin which is excellent in insulating properties and meets the purpose, and has completed the present invention.

That is, the present invention relates to a compound represented by the general formula (I)

[0006]

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(Wherein, Ar ¹ and Ar ^{2 each} represent a hydrogen atom, a halogen atom or a carbon atom which may contain an ether bond)
And represents a divalent aromatic phenol residue having a substituent selected from hydrocarbon groups of 1 to 12, which may be the same or different, and Ar ³ is Ar ¹ or Ar ² . R represents a hydrogen atom or a methyl group, x is 0 or 1,
R ′ represents an aliphatic, alicyclic, substituted or unsubstituted aromatic polyvalent carboxylic acid residue having 2 to 20 carbon atoms, and y is 1 or 2. p, q, and r each represent a mole fraction of a structural unit, and 0.3 ≦ p ≦ 0.6, 0.4 ≦ q ≦ 0.7, 0 ≦ r
≦ 0.3 and p + q + r = 1. ),
An object of the present invention is to provide an alkali-soluble curable resin in which an unsaturated double bond and an alkali-soluble carboxyl group are pendant to a side chain hydroxyl group of a phenoxy resin. The present invention also provides
The side chain hydroxyl groups in the phenoxy resin are added with a predetermined amount of α,
An object of the present invention is to provide a method for producing an alkali-soluble curable resin, which comprises reacting a β-unsaturated monoisocyanate and then a polycarboxylic acid anhydride in this order. Further, the present invention provides, as an α, β-unsaturated monoisocyanate,
An object of the present invention is to provide a method for producing the above-mentioned alkali-soluble curable resin using isocyanate ethyl methacrylate. Still further, the present invention provides a method for producing the alkali-soluble curable resin, wherein the polyvalent carboxylic anhydride is selected from the group consisting of polybasic anhydrides containing trimellitic anhydride. . The present invention also provides a method for producing the alkali-soluble curable resin, wherein the reaction is performed in an aprotic organic solvent. Further, the present invention provides an alkali-soluble curable resin composition obtained by blending the above-mentioned alkali-soluble curable resin with a radical initiator, a crosslinking monomer and / or a curing agent. Furthermore, the present invention provides at least one selected from the group consisting of an organic or inorganic filler, a colorant and an organic solvent.
An object of the present invention is to provide the above-mentioned alkali-soluble curable resin composition comprising at least one kind. Further, according to the present invention, the alkali-soluble curable resin has a number average molecular weight (Mn) of 2000.
As described above, the correlation coefficient ε with the molecular weight distribution represented by the following equation
The use of a phenoxy resin having a molecular weight of 2000 to 20,000 provides the above-mentioned alkali-soluble curable resin composition. Mn = ε (Mw / Mn) where Mn is the number average molecular weight of the phenoxy resin,
Mw is the weight average molecular weight of the phenoxy resin. Furthermore, the present invention provides an alkali-soluble curable resin having an acid value of 100 to 100.
The present invention provides the above-mentioned alkali-soluble curable resin composition, which has a solid content of 200 (mgKOH / g solid content). Furthermore, the present invention provides the above-mentioned alkali-soluble curable resin composition comprising a polyfunctional vinyl polymerizable monomer as a crosslinking monomer and a polyvalent epoxy compound as a curing agent. The present invention also provides a film molded product obtained by removing a solvent from the curable resin or the composition.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The phenoxy resin of the present invention is, as is known, (for example, "New heat-resistant polymer" translated by Iwakura et al.
17, 1971), a polyhydroxy polyether resin obtained by a polyaddition reaction between a bisphenol compound and a bisepoxy compound. Examples of commercially available products include Epotote YP-50, YP-50S (manufactured by Toto Kasei), UCAR, PKHC, PKHH (manufactured by Union Carbide), and the like. The phenoxy resin used in the present invention is not limited to the above-mentioned commercially available products, and a phenoxy resin having a desired structure can be obtained by a polyaddition reaction of various bisphenol compounds and a bisepoxy compound described later. Bisphenol compounds and bisepoxy compounds, which are raw materials for phenoxy resins, are also known per se and can be obtained as commercial products. For example, bisphenol compounds include bisphenol A, bisphenol S, bisphenol SH, bisphenol F, bisphenol Z (manufactured by Mitsubishi Chemical), hydroquinone, resorcin, biphenol, hexafluoroisopropylidene diphenol, dihydroxynaphthalene, tetramethylbiphenol, and dicyclopentadiene modified. Bisphenol and the like. or,
The bisepoxy compound is a diglycidyl ether compound derived from the above-mentioned bisphenol compound and epichlorohydrin. For example, when bisphenol A is used as a raw material, trade names such as Epicoat 828, Epicoat 1001, Epicoat 1004 (all oil-based shell epoxy Manufactured), EPOMIC R-140P, EPOMIC R
-301 (manufactured by Mitsui Petrochemical). For example, when the bisphenol compound is bisphenol A and the bisepoxy compound is bisphenol A diglycidyl ether, a polyaddition product represented by the following formula (II) is useful as an intermediate of the resin of the present invention.

[0009]

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The production conditions and the like of the phenoxy resin are selected according to a known method. For example, known catalysts of various alkalis can be used as the catalyst. Particularly, as the solvent used in the synthesis, the following ones are preferably used in consideration of the addition reaction conditions described later. These solvents described below may be used alone or in combination. Specifically, ethyl methyl ketone, M
Ketones such as IBK, mesityl oxide, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, butyl carbyl Tall acetate, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, γ-butyrolactone and acetic acid ester of the glycol ethers, Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol, benzene, toluene,
Aromatic hydrocarbons such as xylene, dioxane, ethers such as dibutyl ether, etc., dimethylformamide,
Examples include amides such as dimethylacetamide and N-methylpyrrolidone, dimethylsulfoxide, and pyridine, which have good compatibility with resins and a boiling point of 100 to 260.
Those in the range of ° C are preferred. When the boiling point is lower than 100 ° C., it takes a long time to obtain a high molecular weight polymer, which is industrially disadvantageous. Further, when the solution of the obtained alkali-soluble curable resin is desolvated to form a film, it is often difficult to obtain a film having a uniform thickness. On the other hand, boiling point 26
When using a solvent at 0 ° C or higher, temperature control is difficult and
There is a drawback that the high-temperature reaction is violent and gelation is easy, and branching is liable to occur particularly when the molecular weight is increased, and the molecular weight distribution is widened.

In consideration of the performance of a film molded product of the resin of the present invention and a cured product thereof described below, the phenoxy resin has a number average molecular weight of Mn = 2000 or more, preferably Mn.
It is desired that n = 5000 to 20,000 and the molecular weight distribution coefficient ε represented by the following formula is 2,000 to 20,000. Mn = ε (Mw / Mn) where Mn is the number average molecular weight of the phenoxy resin,
Mw is the weight average molecular weight of the phenoxy resin. By using such a phenoxy resin, the formability of the film or sheet is good, and the resulting film or sheet does not easily break and has excellent toughness in handling. When the molecular weight is Mn 2,000 or less, various properties suitable for the purpose, such as film formability, resin curability, solvent resistance, toughness, and solder heat resistance, cannot be satisfied in a well-balanced manner. The higher the molecular weight, the more the various physical properties tend to be improved. However, those having Mn of 20,000 or more are difficult to produce and have problems such as an excessively long reaction time.

On the other hand, another important point of the phenoxy resin of the present invention is the molecular weight distribution. With respect to the molecular weight distribution, the molecular weight distribution generally tends to increase as the molecular weight increases. When synthesizing the phenoxy resin of the present invention, it is possible to select a solvent having a low boiling point and lower the reaction temperature as much as possible until the number average molecular weight Mn is 8000, and to suppress the spread of the molecular weight distribution by slightly increasing the reaction time. It is. However, it is necessary to increase the molecular weight of the resin as much as possible in order to obtain better physical properties,
When the number average molecular weight Mn is 8000 or more, especially when it exceeds 10,000, the molecular weight distribution rapidly and largely expands in most cases, and it is necessary to take measures to suppress it.

In the present invention, the performance of the phenoxy resin and
The relationship between the molecular weight and its distribution can be explained by the correlation coefficient ε shown in the above equation. Average molecular weight Mn is 100
If the value exceeds 00 and the coefficient ε is 2000 or less, that is, if the molecular weight distribution is considerably wide, the effect of increasing the molecular weight of the phenoxy resin after curing cannot be obtained. For example, the strength and toughness of the film may be unbalanced, or the curability and alkali developability may be insufficient. As a device for narrowing the molecular weight distribution, there is 1) the above-mentioned solvent selection. That is, the reaction is carried out by using a solvent having a low boiling point corresponding to the designed molecular weight as much as possible and refluxing at the boiling point of the solvent. More preferably, 2) a method of reacting a bisepoxy compound in several stages. Specifically, first
At the stage, a part of the bisepoxy compound is reacted with the entire amount of the bisphenol compound, and after the reaction has considerably progressed, the remaining bisepoxy compound is added stepwise to complete the reaction, but also adjust the solvent dilution as appropriate And a further effect can be obtained. Conversely, when the entire amount of the bisepoxy compound is reacted with a part of the bisphenol compound in the first stage, and the remaining bisphenol compound is post-added, the molecular weight distribution is rather widened, which is unsuitable.

As the α, β-unsaturated monoisocyanate used for imparting curability in the present invention, methacryloyl isocyanate (manufactured by Nippon Paint) and isocyanateethyl methacrylate (manufactured by Showa Denko) are preferably used. An isocyanate group at one end of the α, β-unsaturated monoisocyanate undergoes an addition reaction with a hydroxyl group of the phenoxy resin, and a methacryloyl group is introduced into the pendant of the phenoxy resin as an unsaturated group for curing. The structural formula is shown below.

[0015]

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(Wherein, Ar ¹ and Ar ^{3 each} represent a hydrogen atom, a halogen atom or a carbon atom which may contain an ether bond)
And represents a divalent aromatic phenol residue having a substituent selected from hydrocarbon groups of 12 to 12, which may be the same or different. R represents a hydrogen atom or a methyl group;
Or 1. p and r each indicate a mole fraction of a structural unit. )

The amount of the α, β-unsaturated monoisocyanate to be used is at least 0.3 mole fraction per hydroxyl group in the phenoxy resin, preferably 0.4 to 0.6 mole fraction.
The amount of the α, β-unsaturated monoisocyanate used depends on the molecular weight and molecular weight distribution of the phenoxy resin used, the type and amount of polycarboxylic anhydride used, the developability with aqueous alkali, and the mechanical toughness of the cured product. Because it is determined from required conditions such as sex, it can not be specified unconditionally,
As shown by the above structural formula, when m is less than 0.3, the photosensitivity is low and the solvent resistance of the cured product is not sufficient. On the other hand, if the amount exceeds 0.6, the amount of hydroxyl groups required for the formation of an acid pendant in the next step required for development with an aqueous alkali is reduced, so that aqueous alkali developability is undesirably reduced.
Further, although it differs slightly depending on the molecular weight of the phenoxy resin, it is necessary to balance the addition of isocyanate ethyl methacrylate and acid anhydride. That is, if the molecular weight of the resin is high, it is necessary to increase the addition of an acid anhydride as much as possible to ensure alkali solubility. Conversely, when the molecular weight of the resin is low, it is necessary to design to add isocyanatoethyl methacrylate as preferentially as possible.

In order to make the hydroxyl groups in the phenoxy resin react with the α, β-unsaturated monoisocyanate under uniform conditions,
It is preferable to carry out in the presence of a solvent. In this case, as the solvent to be used, any aprotic organic solvent can be used, but it is preferable to use the solvent used at the time of synthesizing the phenoxy resin. Further, in consideration of the content of the reaction, it is desirable that the solvent used is sufficiently dehydrated in advance. In the α, β-unsaturated monoisocyanate addition reaction with a hydroxyl group in the phenoxy resin, a catalyst may or may not be present. Since it has high reactivity like methacryloyl isocyanate, the addition reaction easily occurs with phenoxy resin even at room temperature without a catalyst.However, when a catalyst is used to shorten the time and efficiently react, dibutyltin dilaurate, dibutyltin -2-Ethylhexoate, DAB
Normal urethanization catalysts such as CO are preferably used, and the amount and reaction temperature can be within known ranges. Further, polymerization inhibitors to suppress undesirable polymerization side reactions, for example, hydroquinone, benzoquinone, phenothiazine,
It is convenient to carry out the reaction in the presence of resorcin, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, Cu powder and the like.

In the present invention, in order to impart developability with an aqueous alkali, a polycarboxylic anhydride is pendant to the hydroxyl group of the phenoxy resin. The polycarboxylic anhydride used as a raw material for the acid pendant reaction is an aliphatic, alicyclic, substituted or unsubstituted aromatic polycarboxylic anhydride having 2 to 20 carbon atoms. Are maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride,
Examples thereof include 3- or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, chlorendic anhydride, dodecenylsuccinic anhydride, trimellitic anhydride, and pyromellitic anhydride. In particular, in order to impart sufficient aqueous alkali developability, the pendant of the addition reaction product must contain a carboxyl group-containing polybasic anhydride such as trimellitic anhydride, which allows simultaneous addition of two carboxyl groups. Is preferred. These carboxyl group-containing polybasic anhydrides may be used alone or in combination with the other polycarboxylic anhydrides described above.
A combination of more than two types may be used.

The amount of the polycarboxylic acid anhydride used is preferably from 0.4 to 0 based on 1 mole fraction of hydroxyl groups in the phenoxy resin in view of the above-mentioned addition amount of α, β-unsaturated monoisocyanate. 0.7 mole fraction. If the addition amount of the acid anhydride is less than 0.4 mol fraction, sufficient aqueous alkali developability cannot be obtained, and a higher addition amount of the polycarboxylic acid anhydride is desired. Since the addition amount of .beta.,. Beta.-unsaturated monoisocyanate is at least 0.3 mol fraction, the upper limit for the addition of the acid anhydride is 0.7 mol fraction.

Depending on the type and combination of the acid anhydrides, the acid value of the finally obtained reactant is 100 (mg KO).
H / g solid content) or more, preferably 100 to 20
0 (mg KOH / g solids). The acid value is 100 (m
When the amount is less than (gKOH / g solid), the aqueous alkali developability is poor. However, as described above, the acid value is 200 (mgKOH / g solid) as an upper limit on the assumption that the photocurability is secured. To smoothly promote the reaction between the acid anhydride and the hydroxyl group,
It is useful to use known catalysts such as tertiary amines, imidazoles, and metal compounds such as quaternary ammonium, lithium, chromium, and manganese in necessary amounts, and the type and amount of use are selected within known and public ranges. .

Similarly, it is preferable to use a solvent in order to carry out the reaction uniformly. The solvent used may be different from the solvent used in the synthesis of the phenoxy resin and / or the reaction of the α, β-unsaturated monoisocyanate with the phenoxy resin, but may be used commonly in a series of reactions. It is economical to select a solvent.

In the addition reaction between the phenoxy resin and the α, β-unsaturated monoisocyanate and / or polycarboxylic anhydride, the resin concentration is 10 to 70% by weight, preferably 20 to 50% by weight. If the resin concentration is less than 10% by weight, an excessive amount of solvent requires a large amount of energy to remove the solvent, which is not preferable. On the other hand, when the content exceeds 70% by weight, the viscosity of the resin solution is extremely high, so that undesirable reactions such as local heat generation tend to occur. If necessary, a useful method for reducing the viscosity by diluting the solvent during the reaction can be used.

In order to produce an aqueous alkali-soluble curable resin having the structure of the above general formula (I), the reaction with the phenoxy resin is carried out in the order of α, β-unsaturated monoisocyanate and polycarboxylic anhydride. It is important to do with The structure obtained by the reaction order differs depending on the order, and the above-mentioned production conditions and the like may not be applicable.

Based on the alkali-soluble curable resin obtained by the present invention, a radical initiator, a crosslinking monomer and / or a curing agent are blended, and if necessary, an organic or inorganic filler, a coloring agent and an organic An alkali-soluble curable resin composition obtained by blending at least one selected from the group consisting of solvents can be used.

Since the resin of the present invention has an unsaturated group in the side chain, it has thermosetting properties and radiation curing properties by itself.
By adding a photoinitiator, photosensitivity to ultraviolet light, visible light, and infrared light can be imparted. In active energy ray curing, for example, photocuring using ultraviolet light, visible light, infrared light, laser light, or the like, many photoinitiators corresponding to the wavelength are marketed and appropriately selected. To list them, for example, benzoins such as benzoin, furoin, benzoin methyl ether, benzoin isoproether, and benzoin alkyl ethers, acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-monforino-propane-1,2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butane-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-
Anthraquinones such as chloroanthraquinone and 2-aminoanthraquinone, 2,4-dimethylthioxanthone,
Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, benzyls such as benzyl and benzyldimethylketal, benzophenone, 4,4′-dichlorobenzophenone, and 4,4′- Examples include benzophenones such as bisdiethylaminobenzophenone and Michler's ketone, and xanthones. These photoinitiators can be used in a mixture of two or more kinds. The amount of the photoinitiator used is 0.1% by weight or more based on the resin,
Preferably it is in the range of 1% to 10% by weight. When the amount of the photoinitiator is less than 0.1% by weight, the curability at the time of curing is insufficient. On the other hand, when the amount exceeds 10% by weight, not only the effect of increasing the amount is not recognized, but also Not only is the physical property of the product reduced, but it is not economical. In addition, as a light source that emits an active energy ray, a publicly known lamp such as a low-pressure, medium-pressure, high-pressure mercury lamp, a halogen lamp, and a metal halide lamp is used.

Various known monofunctional or polyfunctional (meth) acrylate compounds and the like can be added as a crosslinkable monomer depending on the application, including the improvement of the performance of the cured product. Representative examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol,
Mono- or diacrylates of glycols such as hexanediol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminos such as N, N-dimethylaminoethyl acrylate Alkyl acrylates, polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate and the like, and polyhydric acrylates of ethylene oxide or propylene oxide adduct thereof, phenoxy Acrylate, bisphenol A
Diacrylates and acrylates of these phenols such as ethylene oxide or propylene oxide adducts, glyceryl diglycidyl ether, acrylates of glycidyl ethers such as trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine acrylate; And / or methacrylates for the above acrylates. Examples of the oligomer include various monomers commonly used in photocurable resin compositions such as epoxy acrylate, acid pendant epoxy acrylate, urethane acrylate, and acid pendant urethane acrylate. The amount of these crosslinkable monomers used varies depending on the use, the method of use, the type of crosslinkable monomer, and the compatibility with the resin of the present invention.
Although it cannot be specified unconditionally, 0 to 100 parts by weight of resin
It is 300 parts by weight, preferably 0 to 200 parts by weight. When the added amount exceeds 300 parts by weight, when used as a dry film, the crosslinked monomer added often easily oozes out of the resin, causing stickiness of the surface and the like,
Not preferred.

Other crosslinking monomers include, for example,
When the residual carboxyl group in the cured resin becomes unnecessary depending on the purpose of use, for example, when used for a solder resist ink film or a build-up laminated film, a polyvalent epoxy compound or a polyvalent epoxy compound is used as employed in the solder resist method. Oxazoline, amino resin, etc. can be used together for encapsulation. If alkali-soluble modification is required, use styrene-maleic acid resin, etc., or use hydroxyalkyl (meth) acrylate and acid anhydride as monomers. It can also be used in combination with a half ester of the above depending on the use. These amounts can be defined from the acid value of the resin.

The alkali-soluble curable resin of the present invention and / or the composition thereof may be optionally coated with extender pigments and dyes to form a coating.

The alkali-soluble curable resin of the present invention and / or
Alternatively, the composition can be used not only as a liquid resist material as a solution in the above-mentioned various applications but also as a dry film after removing the solvent. Filming is applied on a smooth surface that can be released,
The solvent is volatilized by an ordinary casting method at a low temperature in an environment where light is shielded as much as possible, and a film having a desired film thickness can be obtained.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
The synthesis example of the phenoxy resin is shown below.

Synthesis Example 1 Using a 500 ml four-neck separable flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 114 g of bisphenol A was added to 201 g of mesityl oxide (manufactured by Wako Pure Chemical Industries) as a solvent. (Mitsubishi Chemical,
Molecular weight = 228.3) and 188 g of epomic R-14
After charging 0P (manufactured by Mitsui Petrochemical Co., epoxy equivalent = 188) and 0.56 g of solid KOH, the temperature is gradually increased while stirring to about 50 ° C., and dissolved until the appearance becomes transparent. Thereafter, the mixture was heated up to a boiling point of mesityl oxide of 126 ° C., kept for about 2 hours, and reacted. Thereafter, the heating was once stopped, and after cooling to 110 ° C., 168 g of mesityl oxide was further added and diluted. The temperature was raised again to the boiling point of mesityl oxide of 126 ° C., and the mixture was refluxed for about 2 hours. The obtained resin liquid was put into cold water with vigorous stirring, and then a precipitate was obtained by standing still. The precipitate was vacuum-dried at 60 ° C. or lower for 10 hours to produce a pale yellow solid phenoxy resin. GPC measurement using the phenoxy resin thus obtained (Showex DPC, Shodex GPC S
ystem-21, using an eluent of tetrahydrofuran, an elution rate of 1 ml / min, a measurement temperature of 40 ° C., and standard polystyrene conversion), the molecular weight (Mn) was 1600.
At 0, the distribution coefficient ε was 3478. Also, the phenoxy resin was prepared using a DSC (manufactured by RIGAKU, DSC82).
30) or Vibron (Orientec, Rheo
Vibron Model DDV-25FP) measured a glass transition temperature around 100 ° C. Further, the chemical structure of the obtained alkali-soluble curable resin of the present invention was measured by ¹³ C-NMR (JEOL).
And JNM-LA300), the assignment of carbon could be specified, and it was confirmed that the structure was a structure represented by the formula (II) (FIG. 1). The same confirmation is performed for all the following synthesis examples.

Synthesis Example 2 Using a 500 ml four-neck separable flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 75.5 g of methyl ethyl ketone (ME
K) and 114 g of bisphenol A (manufactured by Mitsubishi Chemical Corporation, molecular weight = 228.3) and 188 g of epomic R-140P
(Manufactured by Mitsui Petrochemical, epoxy equivalent = 188);
After charging 56 g of solid KOH, the temperature is increased while gradually stirring to about 50 ° C., and dissolved until the appearance becomes transparent. Then, the mixture is heated to a boiling point of 80 ° C. of MEK and maintained for about 8 hours to complete the reaction. The obtained resin liquid was put into cold water with vigorous stirring, and then a precipitate was obtained by standing still. The precipitate was vacuum dried at 50 ° C. or lower for 6 hours to produce a white solid phenoxy resin. The molecular weight (Mn) of the obtained phenoxy resin was 5,500 and the distribution coefficient ε was 2619.
Met.

Synthesis Example 3 Using a 500 ml four-neck separable flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 104 g of diethylene glycol monoethyl ether acetate (ECA / Kanto Chemical) was used as a solvent.
14 g of bisphenol A (manufactured by Mitsubishi Chemical Corporation, molecular weight = 22
8.3), 476 g of Epomic R-301 (manufactured by Mitsui Petrochemicals, epoxy equivalent = 476), and 2.62 g of triphenylphosphine, and then the temperature was gradually increased while stirring to about 50 ° C., Dissolve until transparent in appearance. Then, the mixture was heated to a boiling point of 200 ° C. of ECA, held for about 2 hours, and reacted. Thereafter, the heating was stopped once, and the mixture was cooled to 180 ° C., and 290 g of ECA was further added and diluted, and the mixture was further cooled to 80 ° C. or lower while stirring.
The obtained resin liquid was put into cold water with vigorous stirring, and then a precipitate was obtained by standing still. The precipitate was vacuum-dried at 50 ° C. or lower for 6 hours to produce a pale yellow solid phenoxy resin. The molecular weight (Mn) of the obtained phenoxy resin is 100
00, and the distribution coefficient ε was 3030.

Synthesis Example 4 Using a 500 ml four-neck separable flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 164 g of mesityl oxide (manufactured by Wako Pure Chemical Industries) as a solvent and 114 g of bisphenol A were used. (Mitsubishi Chemical,
Molecular weight = 228.3) and 131.6 g of epomic R-
140P (Mitsui Petrochemical, epoxy equivalent = 188),
And 0.392 g of solid KOH,
The temperature is raised while stirring to about 0 ° C. and dissolved until the appearance becomes transparent. Thereafter, the boiling point of mesityl oxide 126
C., and kept for about 2 hours to react. Thereafter, 56.4 g of Epomic R-
140P (Mitsui Petrochemical, epoxy equivalent = 188),
After adding 37.3 g of mesityl oxide and 0.168 g of solid KOH and refluxing for 2 hours, 168 g of mesityl oxide was additionally added and the mixture was further refluxed for 2 hours. The obtained resin liquid was put into cold water with vigorous stirring, and then a precipitate was obtained by standing still. The precipitate was vacuum-dried at 60 ° C. or lower for 10 hours to produce a pale yellow solid phenoxy resin. The molecular weight (Mn) of the obtained phenoxy resin is 150
00, and the distribution coefficient ε was 4166.

Synthesis Example 5 A 500 ml four-neck separable flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel was used. As a solvent, 453 g of cyclohexanone (manufactured by Kanto Chemical) and 114 g of bisphenol A (manufactured by Mitsubishi Chemical) , Molecular weight = 228.3) and 188 g of epomic R-140.
After charging P (manufactured by Mitsui Petrochemical, epoxy equivalent = 188) and 0.56 g of solid KOH, the temperature is increased while gradually stirring to about 60 ° C., and dissolved until the appearance becomes transparent. Thereafter, the boiling point of cyclohexanone is 150 to 155.
Heated to C and refluxed for about 1.5 hours to complete the reaction. The obtained resin liquid was put into cold water with vigorous stirring, and then a precipitate was obtained by standing still. The precipitate was vacuum dried at 60 ° C. or lower for 12 hours to produce a light yellow solid phenoxy resin. The molecular weight (Mn) of the obtained phenoxy resin was 16,000, and the distribution coefficient ε was 1882.

Example 1 After drying the phenoxy resin synthesized in the above Synthesis Example 1 at room temperature and in a vacuum, 56.8 g of a solid resin was taken, and 195.
Dissolved in 3 g of diethylene glycol monoethyl ether acetate (ECA / Kanto Chemical) and further 0.1 g
While adding hydroquinone and maintaining the temperature at 70 ° C, 12.4 g (0.4 mole fraction / -OH
Group) Isocyanate ethyl methacrylate (manufactured by Showa Denko, trade name: Karenz MOI) and a solution of 0.124 g of dibutyltin dilaurate were charged and reacted at 70 ° C. for 90 minutes to complete the reaction. The completion of the addition reaction of the α, β-unsaturated monoisocyanate to the hydroxyl group in the phenoxy resin can be determined by FTIR measurement (260-10 type I manufactured by Hitachi, Ltd.).
It was confirmed by the complete disappearance of the absorption peak (near 2250 cm ^-1 ) due to the -NCO group (R spectrophotometer) (FIG. 2 = after addition of MOI, FIG. 3 after completion of MOI addition reaction). In addition, ¹³ C-N
An MR measurement (same as above) was carried out, and 155.857 ppm (N
o. 1) The appearance of a new peak was observed in the vicinity, confirming that the -O-CO-NH- bond was generated (Fig. 4). Hereinafter, the same confirmation is performed for all the examples. Next, a solution in which 23.04 g (0.6 mole fraction / -OH group in resin) of trimellitic anhydride (TMA, manufactured by Kanto Chemical Co.) was previously dissolved in 81.4 g of ECA, and triethylamine (TEA) as a catalyst. Was added, and the addition reaction was completed while maintaining the temperature at 95 to 97 ° C. and confirming the end point by FTIR. The acid value of the obtained resin was 142 (mgKOH / g). The confirmation of the addition reaction of the polycarboxylic acid anhydride to the hydroxyl group of the phenoxy resin was carried out by FTIR measurement (Hitachi Ltd., 26
The end point was determined by observing the decrease in the absorption peak (around 1780 cm ^-1 ) due to the acid anhydride group with a 0-10 type IR spectrophotometer (FIG. 5 = after addition of TMA, FIG. 6 = end of TMA addition reaction). rear). The reaction product was subjected to ¹³ C-NMR measurement, and 165.974 ppm
A peak attributable to the carbonyl group in the -O-CO-Ar- bond was observed near (No. 2), confirming that the polycarboxylic anhydride was opened and added to the hydroxyl group of the phenoxy resin. (FIG. 4). In other words, with the phenoxy resin alone, each of the carbon assignments could be specified as shown in FIG. 2, and in comparison with this, this reaction product was newly attributed to the carbonyl group as shown in FIG. Many peaks appear. The assignment was analyzed, and the results were specified as summarized in Table 1, and it was confirmed that the results matched the structure represented by the formula (I). The same confirmation is performed for all the following synthesis examples. To the resin solution thus obtained, 2% by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba-Geigy, trade name: Darocure 1173) was added as a photoinitiator to the resin solid content. And
A sample for light curing was used.

[0038]

[Table 1]

Example 2 The phenoxy resin synthesized in Synthesis Example 2 was reacted in the same manner as in Example 1. The acid value of the product is 132 (mg KOH /
g).

Example 3 The phenoxy resin synthesized in Synthesis Example 3 was reacted in the same manner as in Example 1. The acid value of the product is 140 (mg KOH /
g).

Example 4 The phenoxy resin synthesized in Synthesis Example 4 was reacted in the same manner as in Example 1. The acid value of the product is 137 (mg KOH /
g).

Example 5 The phenoxy resin synthesized in Synthesis Example 1 was reacted with MOI in the same manner as in Example 1, and as an acid anhydride, 11.52 g of trimellitic anhydride (TMA, manufactured by Kanto Chemical Co., Ltd.) was used. Mole fraction / -OH group in resin) and 6.0 g of succinic anhydride
(0.3 mole fraction / -OH group in resin). The acid value in this case was 116 (mgKOH / g).

Example 6 Epotote YP-50S as a commercially available phenoxy resin
(Toto Kasei, Mn = 15000, Mw / Mn = 4.
Example 1 except that 16.8 was used as a solid in 56.8 g.
Reacted in the same manner as. The acid value of the product is 135 (mgK
OH / g).

Example 7 The resin solution of the present invention obtained in Example 1 was further added with trimethylolpropane triacrylate (TM
PTA, manufactured by Osaka Organic Chemical Industry) was added so as to be 20% by weight based on the solid content of the resin.

Example 8 Epoxy R-140P (manufactured by Mitsui Petrochemical, epoxy equivalent =
188) was added so as to be 0.5 equivalent to the acid value of the resin.

Comparative Example 1 A phenoxy resin synthesized in Synthesis Example 5 was dried and reacted in the same manner as in Example 1 except that 56.8 g of the obtained solid content was used. The acid value for the product is 127 (mg
KOH / g).

Comparative Example 2 6.2 g (0.2 mol fraction / -OH group in resin) of isocyanate ethyl methacrylate (manufactured by Showa Denko, trade name Karenz MOI) and trimellitic anhydride (TMA / Kanto Chemical) were used. 26.88 g (0.7 mole fraction / -OH in resin)
Except that the reaction was carried out in the same manner as in Example 1. The acid value for the product was 170 (mg KOH / g).

Comparative Example 3 12.4 g of isocyanateethyl methacrylate (manufactured by Showa Denko, trade name: Karenz MOI) (0.4 mole fraction /
11.52 g (0.3 mol fraction / -O in resin) of trimellitic anhydride (TMA / Kanto Chemical)
The reaction was carried out in the same manner as in Example 1 except that H was used. The acid value for the product was 83 (mg KOH / g).

Comparative Example 4 As an acid anhydride, 12.0 g of succinic anhydride (manufactured by Kanto Kagaku) in place of trimellitic anhydride (0.6 mole fraction /
The reaction was carried out in the same manner as in Example 1 except that (-OH group in the resin) was used. The acid value for the product is 83 (mg KO
H / g).

Comparative Example 5 Instead of the phenoxy resin, epoxy acrylate Lipoxy SPB-37-5X (manufactured by Showa Polymer, Mn = 1)
300, Mw / Mn = 1.9) was used as a comparison, and the acid value in this case was 98 (mg KOH / g).

The resins and compositions obtained in the above Examples 1 to 8 and Comparative Examples 1 to 5 were applied to a copper foil substrate using an applicator so as to have a predetermined thickness.
After drying for 0 minutes, it was used as an evaluation sample. The results of testing the physical properties of these coating films are shown in Tables 2 and 3, respectively. In addition, the test method of various performances and evaluation judgment are as follows.

1. Photosensitivity test Using ultraviolet light with a wavelength of 365 nm (manufactured by Iwasaki Electric Co., ultraviolet curing device, lamp H2000LU-1), 5 passes in one pass.
10 times with 0 mJ / cm ² irradiation light amount (total 500 mJ / c
m ² ) After passing irradiation, solvent methyl ethyl ketone (ME
K) was dropped, and the swelling state of the coating film surface was visually determined. ○ No change is observed △ Surface is slightly swollen × Surface is significantly swollen

2. Developability test A test piece was irradiated with ultraviolet light having a wavelength of 365 nm through a photomask and passed 15 times (750 mJ / cm ^{2 in} total) with the above-mentioned irradiation light amount. A test piece was prepared by using an aqueous solution of 1% by weight of NaOH as a developer. After development at 60 ° C. for 60 seconds with a spray pressure of about 0.8 kg / cm ² (spray developing device manufactured by Nissin Seisakusho), the state where unexposed portions were removed was visually judged. ○ Completely developed △ Underdeveloped parts on the surface × Undeveloped whole

3. Adhesion test 365n of coating film (about 30μm) formed on copper foil substrate
A test piece was irradiated with ultraviolet light having a wavelength of m and passed through 15 times (750 mJ / cm ^{2 in} total) with the above-mentioned irradiation light amount. A test piece was cut in a grid pattern in accordance with the test method of JIS D0202, and then a cellophane tape was used. The state of peeling after the peeling test was visually determined. ○ 100/100 with no peeling △ △ 100/100 with slightly peeled cross cut × 90/100 or less

4. Solvent Resistance Test The same test piece as in the adhesion test was immersed in acetone and methyl ethyl ketone (MEK) for 30 minutes at room temperature, then taken out, and the state of the coating film and the adhesion were comprehensively evaluated. ○ No change observed △ Slight change × Notable change

5. Tensile strength measurement Casting the resin solution on PET film
After drying with hot air at 2 ° C. for 2 hours, it was left at room temperature for 1 hour to obtain a thin film having a thickness of about 50 μm. Irradiate with ultraviolet light having a wavelength of 365 nm, and 15 times (750 mJ / cm ^{2 in} total) with the above-mentioned irradiation light amount
Let it pass. Width 10.0 for thin film before and after UV irradiation
mm and a length of 50 mm to obtain a test piece.
Tensilon (Orientec, TENS)
Using ILONUTM-10T), pulling speed 100mm
/ Min.

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

The alkali-soluble curable resin obtained by the present invention has curability comparable to general thermosetting resins such as unsaturated polyester resins and vinyl ester resins, and has an aqueous alkali developability. It is possible and has excellent heat resistance, toughness and solvent resistance. Not only is it useful as a resist for circuit formation by the build-up method described above, it is also useful for forming partition walls for plasma displays, etching resists for metals and glass, photoelectroforming resists, resists for printing plates, resists for wiring processing, etc. It is extremely useful as a base resin for microfabrication resists in various applications such as electrical appliances, electronic components, and measuring instruments.

[Brief description of the drawings]

FIG. 1 is a diagram showing the results of ¹³ C-NMR measurement of the resin obtained in Synthesis Example 1.

FIG. 2 is a diagram showing FTIR measurement results after MOI was added to the phenoxy resin of Example 1.

FIG. 3 is a diagram showing FTIR measurement results after the completion of the MOI addition reaction to the phenoxy resin of Example 1.

FIG. 4 is a diagram showing the results of ¹³ C-NMR measurement after the completion of the MOI addition reaction to the phenoxy resin in Example 1.

FIG. 5 is a diagram showing FTIR measurement results after adding TMA to the phenoxy resin of Example 1.

FIG. 6 is a diagram showing the results of FTIR measurement after the completion of the TMA addition reaction to the phenoxy resin of Example 1.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5/00 C08K 5/00 C08L 71/00 C08L 71/00 A G03F 7/027 513 G03F 7/027 513 (72) Inventor Toshiaki Hanida 1019-1 Tomizuka-cho, Isesaki-shi, Gunma Inside Showa Takashige Co., Ltd.

Claims (11)

[Claims] 1. A compound of the general formula (I) (Wherein, Ar ¹ and Ar ² represent a divalent aromatic phenol residue having a substituent selected from a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may contain an ether bond, May be the same or different from each other,
r ³ is Ar ¹ or Ar ² . R represents a hydrogen atom or a methyl group, x is 0 or 1, and R ′ has 2 carbon atoms.
Represents up to 20 aliphatic, alicyclic, substituted or unsubstituted aromatic polyvalent carboxylic acid residues, and y is 1 or 2. p,
q and r each represent a mole fraction of a structural unit, and 0.3 ≦ p ≦
0.6, 0.4 ≦ q ≦ 0.7, 0 ≦ r ≦ 0.3, and p
+ Q + r = 1. (2) An alkali-soluble curable resin in which an unsaturated double bond and an alkali-soluble carboxyl group are pendant to the side chain hydroxyl group of the phenoxy resin. 2. An alkali which is reacted with a side chain hydroxyl group in the phenoxy resin according to claim 1 in the order of a predetermined amount of an α, β-unsaturated monoisocyanate and then a polycarboxylic anhydride. A method for producing a soluble curable resin. 3. The method for producing an alkali-soluble curable resin according to claim 2, wherein isocyanate ethyl methacrylate is used as the α, β-unsaturated monoisocyanate. 4. The method for producing an alkali-soluble curable resin according to claim 2, wherein the polycarboxylic anhydride is selected from the group consisting of polybasic anhydrides containing trimellitic anhydride. 5. The method for producing an alkali-soluble curable resin according to claim 2, wherein the reaction is performed in an aprotic organic solvent. 6. An alkali-soluble curable resin composition comprising the alkali-soluble curable resin according to claim 1 and a radical initiator, a crosslinkable monomer and / or a curing agent. 7. The alkali-soluble curable resin composition according to claim 6, wherein at least one selected from the group consisting of an organic or inorganic filler, a colorant and an organic solvent is blended. 8. As the alkali-soluble curable resin, a phenoxy resin having a number average molecular weight (Mn) of 2,000 or more and a correlation coefficient ε with a molecular weight distribution represented by the following formula of 2,000 to 20,000 is used. The alkali-soluble curable resin composition according to claim 6 or 7, wherein Mn = ε (Mw / Mn) where Mn is the number average molecular weight of the phenoxy resin,
Mw is the weight average molecular weight of the phenoxy resin. 9. An alkali-soluble curable resin having an acid value of 10
The alkali-soluble curable resin composition according to any one of claims 6 to 8, wherein the composition is 0 to 200 (mgKOH / g solid content). 10. The alkali-soluble curable resin according to claim 6, wherein a polyfunctional vinyl polymerizable monomer is blended as a crosslinking monomer and a polyvalent epoxy compound is blended as a curing agent. Composition. 11. A film molded product obtained by removing a solvent from the curable resin according to claim 1 or the composition according to any one of claims 6 to 10.