JP2008144027A - Resin composition and photosensitive resin composition containing the resin composition and method for producing the resin composition and the photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition containing a modified polymer having a carboxy group on the side chain while having adequate molecular weight and a photosensitive resin composition containing the resin composition and to provide a production method efficiently producing the resin composition and the photosensitive resin composition. <P>SOLUTION: The resin composition comprises a modified polymer (I) having a carboxy group on the side chain and obtained by reacting at least a part of hydroxy groups of a hydroxy group-containing polymer obtained by using a hydroxy group-containing monomer as an essential component in the presence of a thiol compound with a polybasic acid anhydride, and a reaction product of a compound reacting with a thiol group with the thiol compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition containing a modified polymer having a carboxyl group in a side chain, a photosensitive resin composition containing the resin composition, and a method for producing the resin composition and the photosensitive resin composition.

  Photosensitive resins can be finely processed by applying the principle of photolithography (photolithography), and can form images by giving cured products with excellent physical properties. It is widely used for applications such as plates. Photosensitive resins include a solvent development type and an alkali development type. In recent years, an alkali development type that can be developed with a dilute weak alkaline aqueous solution has become mainstream from the viewpoint of environmental measures. For example, alkali-developable photosensitive resins are used in printed wiring board manufacture, liquid crystal display board manufacture, printing plate making, and the like.

  When using a photosensitive resin, for example, as a liquid development type solder resist resin in a photolithography process, the photosensitive resin is first applied on a substrate, followed by heat drying to form a coating film. After that, a series of steps are adopted in which a film for pattern formation is mounted and exposed to this coating film, and then developed.

  In such a process, in order to form a fine pattern with high reliability and good reproducibility, the photosensitive resin is required to have high photosensitivity during exposure. Also, during development, the portion cured by exposure must not be eroded by the developer, and conversely, the unexposed portion must be removed promptly during development. Desired. Furthermore, for the parts cured by exposure, characteristics related to long-term reliability such as heat resistance, water resistance, moisture resistance, etc. that can withstand high processing conditions (soldering process in the case of solder resist, etc.) Is required.

  The present inventors have so far developed a photosensitive resin for image formation that can provide both a sensitivity at the time of exposure and an alkali developability, and can provide a cured product that is excellent in heat resistance but does not exhibit brittleness. (For example, refer to Patent Document 1).

  The photosensitive resin for image formation disclosed in Patent Document 1 is a photosensitive resin composition capable of forming a coating film that can be developed with an alkali, and includes an N-substituted maleimide component (A) and a hydroxyl group-containing monomer. It has a carboxyl group obtained by reacting polybasic acid anhydride (C) with at least a part of the hydroxyl group of polymer (I) obtained by radical polymerization using (B) as an essential component. The modified polymer (II) is contained.

  Here, it is preferable that the molecular weight of the polymer (I) is appropriately adjusted. This is due to the following reason. That is, if the molecular weight of the polymer (I) is large, the alkali developability of the resulting photosensitive resin containing the modified polymer (II) may be lowered. Therefore, it is necessary to increase the acid value of the modified polymer (II) by reacting more polybasic acid anhydride (C). However, when the acid value of the modified polymer (II) is increased, more carboxyl groups are contained in the cured portion after the alkali development of the photosensitive resin, so that the moisture resistance and water resistance of the cured portion are increased. Will be inferior.

Therefore, in order to satisfy various requirements for the photosensitive resin composition with high accuracy, an example of adjusting the molecular weight of the polymer (I) by using a chain transfer agent or the like at the time of preparing the polymer (I) is exemplified. Has been.
JP-A-2005-141011

  However, when a chain transfer agent is used when preparing the polymer (I), the molecular weight of the polymer (I) can be adjusted, but then the polybasic acid anhydride with respect to the hydroxyl group of the polymer (I) Even if it is intended to obtain a modified polymer (II) having a carboxyl group by reacting (C), the polybasic acid anhydride (C) is difficult to react with the hydroxyl group of the polymer (I). I understood.

  As a result of intensive studies by the inventors, when the molecular weight of the modified polymer (I) is adjusted using a chain transfer agent, the polybasic acid anhydride reacts with the hydroxyl group of the modified polymer (I). This is because the catalyst used for the addition reaction of the polybasic acid anhydride to the hydroxyl group is deactivated by the chain transfer agent that could not participate in the adjustment of the molecular weight of the modified polymer (I). And gained knowledge.

  The present invention has been made in view of the above circumstances, and includes a resin composition including a modified polymer having a carboxyl group in a side chain while having an appropriate molecular weight, and a photosensitive resin composition including the resin composition It is an object of the present invention to provide a product and a production method capable of efficiently producing the resin composition and the photosensitive resin composition.

  The resin composition of the present invention has a side chain in which a polybasic acid anhydride is reacted with at least a part of hydroxyl groups of a hydroxyl group-containing polymer obtained by using a hydroxyl group-containing monomer as an essential component in the presence of a thiol compound. It contains a modified polymer (I) having a carboxyl group, a compound that reacts with a thiol group, and a reaction product of the thiol compound.

  As will be described later, the resin composition of the present invention includes a hydroxyl group-containing polymer whose molecular weight is appropriately adjusted by radical polymerization of a monomer component containing a hydroxyl group-containing monomer in the presence of a thiol compound. Obtain a mixture, then add a compound that reacts with the thiol group to this reaction mixture, react with the excess thiol compound that was not involved in adjusting the molecular weight of the polymer, then add more polybasic acid anhydride and catalyst To get by. Therefore, in addition to the modified polymer (I) having a carboxyl group in the side chain, the resin composition of the present invention contains a reaction product of a thiol compound and a compound that reacts with the thiol group.

  Here, examples of the compound that reacts with the thiol group include one or more compounds selected from the group consisting of epoxy compounds, vinyl ether compounds, and vinyl thioether compounds. The compound that reacts with the thiol group is preferably a compound that has both a functional group that reacts with the thiol group and an ethylenically unsaturated double bond in one molecule.

  The hydroxyl group-containing polymer is preferably obtained by further using N-substituted maleimide as an essential component.

  By using N-substituted maleimide as a monomer component, good heat resistance is imparted to the resulting cured polymer. For this reason, according to the above configuration, the modified polymer (I) (or the modified polymer (II) described later) contains a structural unit derived from N-substituted maleimide. A cured product obtained by using the composition has excellent heat resistance.

  The photosensitive resin composition of this invention may be comprised including the said resin composition and the polymeric compound which has an ethylenically unsaturated double bond.

  With this configuration, the photosensitive resin composition of the present invention has alkali developability derived from the carboxyl group of the modified polymer (I) and photopolymerizability derived from the ethylenically unsaturated double bond of the polymerizable compound. You will have both.

  In the photosensitive resin composition of the present invention, the modified polymer (I) has a hydroxyl group and / or a carboxyl group in at least a part of hydroxyl groups and / or a part of carboxyl groups of the modified polymer (I). The side chain is reacted with a compound having a functional group that undergoes an addition reaction and an ethylenically unsaturated double bond in one molecule (hereinafter sometimes simply referred to as “compound A”). A preferred embodiment is a modified polymer (II) further having a bond.

  With this configuration, an ethylenically unsaturated double bond is introduced into the modified polymer (I) via a functional group that undergoes an addition reaction with the hydroxyl group and / or carboxyl group of the compound A. Therefore, the modified polymer (II) obtained by addition reaction of the compound A with the modified polymer (I) has a carboxyl group and an ethylenically unsaturated double bond in one molecule. (II) By itself, it has both alkali developability and photopolymerizability.

  The photosensitive resin composition of the present invention preferably further includes a compound having a functional group that reacts with two or more carboxyl groups in one molecule (hereinafter, sometimes simply referred to as “compound B”).

  With this configuration, the photosensitive resin composition of the present invention has thermosetting properties. Moreover, when the photosensitive resin composition of the present invention is heat-treated, the carboxyl group of the modified polymer (I) or the modified polymer (II) is cross-linked through the compound B.

  The method for producing a resin composition of the present invention includes a step of obtaining a hydroxyl group-containing polymer by mixing and polymerizing components including a thiol compound, a hydroxyl group-containing monomer, and a polymerization initiator, A modified polymer having a carboxyl group in the side chain by further mixing a compound that reacts with a group, a polybasic acid anhydride, and a reaction catalyst of the polybasic acid anhydride and a hydroxyl group; I) is obtained.

  With this configuration, it is possible to prevent the catalyst used for the addition reaction of the polybasic acid anhydride to the hydroxyl group of the hydroxyl group-containing polymer from being deactivated by the thiol compound.

  Here, examples of the compound that reacts with the thiol group include one or more compounds selected from the group consisting of epoxy compounds, vinyl ether compounds, and vinyl thioether compounds. The compound that reacts with the thiol group is preferably a compound that has both a functional group that reacts with the thiol group and an ethylenically unsaturated double bond in one molecule.

  Examples of the reaction catalyst include one or more reaction catalysts selected from the group consisting of tertiary amines, quaternary ammonium salts, imidazole compounds, phosphorus compounds, carboxylic acid metal salts, and inorganic metal salts.

  In the method for producing a resin composition of the present invention, the step of obtaining the hydroxyl group-containing polymer is preferably performed by further mixing and polymerizing an N-substituted maleimide.

  The manufacturing method of the photosensitive resin composition of this invention may be comprised including the process of further mixing the polymeric compound which has an ethylenically unsaturated double bond with the manufacturing method of the said resin composition.

  The method for producing a photosensitive resin composition of the present invention is the method for producing a resin composition, wherein the functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond are present in one molecule. In a preferred embodiment, the method further comprises a step of further mixing the compound to make the modified polymer (I) a modified polymer (II) further having an ethylenically unsaturated double bond in the side chain. is there.

  The method for producing a photosensitive resin composition of the present invention preferably includes a step of further mixing a compound having in one molecule a functional group that reacts with two or more carboxyl groups.

  The present invention includes a resin composition produced by the production method and a photosensitive resin composition.

  Since the (photosensitive) resin composition of the present invention contains a modified polymer having a carboxyl group in the side chain while the molecular weight is appropriately adjusted, it has excellent alkali developability. Moreover, the hardened | cured material excellent in water resistance and moisture resistance was able to be given. Further, by further containing a polymerizable compound having an ethylenically unsaturated double bond or a compound having a functional group that reacts with two or more carboxyl groups in one molecule, not only alkali developability but also at the time of exposure. The sensitivity was also excellent. Furthermore, a cured product having excellent heat resistance and strength could be provided.

  Moreover, according to the manufacturing method of the (photosensitive) resin composition of this invention, the modified polymer which has a carboxyl group in a side chain was able to be manufactured with high efficiency.

(Resin composition)
The resin composition of the present invention has a side chain in which a polybasic acid anhydride is reacted with at least a part of hydroxyl groups of a hydroxyl group-containing polymer obtained by using a hydroxyl group-containing monomer as an essential component in the presence of a thiol compound. It contains a modified polymer (I) having a carboxyl group, a compound that reacts with a thiol group, and a reaction product of the thiol compound. Hereinafter, the resin composition of the present invention will be described.

<Thiol compound>
The thiol compound used in the present invention acts as a chain transfer agent during the polymerization reaction of the monomer component containing the hydroxyl group-containing monomer, and adjusts the molecular weight of the resulting hydroxyl group-containing polymer within a predetermined range. And if it does not have a bad influence on a monomer component, it will not specifically limit. Specifically, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan; aryl mercaptans such as thiophenol; mercapto group-containing aliphatic carboxylic acids such as mercaptopropionic acid and methyl mercaptopropionate and the like Examples include esters. These thiol compounds may be used alone or in combination of two or more.

<Hydroxyl group-containing monomer>
The hydroxyl group-containing monomer used in the present invention is not particularly limited as long as it can introduce a hydroxyl group into the side chain of the polymer obtained by polymerizing the monomer, but it is separated from the main chain of the polymer. A hydroxyl group-containing monomer that retains a hydroxyl group at a position is preferable. According to this embodiment, when the hydroxyl group and polybasic acid anhydride are subjected to an addition reaction to introduce a carboxyl group into the side chain of the polymer (described later), the carboxyl group is located at a position separated from the main chain of the polymer. Will be held. As a result, it is possible to prevent the carboxyl group from being buried in the polymer. For this reason, an uncured coating film (hereinafter sometimes simply referred to as “coating film”) obtained from a (photosensitive) resin composition prepared using this hydroxyl group-containing monomer has good alkali development. Sex can be expressed.

  Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxymethyl (meth) acrylamide, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono ( Examples thereof include hydroxyalkyl vinyl ethers such as (meth) acrylate and 4-hydroxybutyl vinyl ether, allyl alcohol, and p-hydroxystyrene. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

  In particular, the hydroxyl group-containing monomer used in the present invention has a primary alcoholic hydroxyl group or a secondary alcoholic hydroxyl group in which a methyl group or an ethyl group is bonded to an α-position carbon based on the hydroxyl group. What has is preferable, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate etc. are mentioned. These hydroxyl group-containing monomers have good reaction with polybasic acid anhydrides after polymerization, and the carboxyl groups introduced into the polymer as a result of reaction with polybasic acid anhydrides are more sterically hindered. It becomes difficult. Therefore, when such a hydroxyl group-containing monomer is used, the alkali developability of the coating film is further improved.

  When flexibility is required for the cured coating film obtained using the resin composition of the present invention, an alkylene oxide is added to the hydroxyl group-containing monomer as the hydroxyl group-containing monomer used in the present invention. Modified product, “PLAXEL (registered trademark) F” series (manufactured by Daicel Chemical Industries) which is a modified polycaprolactone of 2-hydroxyethyl (meth) acrylate, or 1,18-octadecanedicarboxylic acid or 1,16- Long-chain alcohols such as a reaction product of a long-chain dibasic acid such as (6-ethylhexadecane) dicarboxylic acid and an epoxy group-containing monomer such as glycidyl methacrylate are suitable.

<Hydroxyl group-containing polymer>
The hydroxyl group-containing polymer used in the present invention is obtained by radical polymerization using the above hydroxyl group-containing monomer as an essential component in the presence of a thiol compound that is a chain transfer agent. For this reason, the hydroxyl group-containing polymer has a suitable molecular weight by adding a thiol residue to the end of the main chain, and has a hydroxyl group in the side chain.

  The content of the structural unit derived from the hydroxyl group-containing monomer in the hydroxyl group-containing polymer is preferably 20 mol% or more, and 30 mol%, when all the structural units of the hydroxyl group-containing polymer are 100 mol%. The above is more preferable, 40 mol% or more is more preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, and 80 mol% or less is more preferable. If the content of the hydroxyl group-containing monomer is less than 20 mol%, the amount of hydroxyl groups that undergo addition reaction with the polybasic acid anhydride in the hydroxyl group-containing polymer is reduced, resulting in a hydroxyl group-containing weight. A necessary amount of carboxyl groups cannot be introduced into the side chain of the coalescence. When the content of the hydroxyl group-containing monomer exceeds 95 mol%, the total amount of carboxyl groups and residual hydroxyl groups introduced by the reaction with the polybasic acid anhydride increases. As a result, a cured coating film obtained using such a resin composition may be inferior in moisture resistance and water resistance. In addition, the other monomer which can comprise a hydroxyl group containing polymer is mentioned later.

  The weight average molecular weight (Mw) of the hydroxyl group-containing polymer used in the present invention is gel permeation in consideration of physical properties such as alkali developability of the coating film of the resin composition of the present invention and heat resistance of the cured coating film. The value measured by chromatography (GPC) is preferably 1,000 or more in terms of polystyrene, more preferably 3,000 or more, further preferably 5,000 or more, preferably 50,000 or less, 40,000. The following is more preferable, 30,000 or less is further preferable, and 20,000 or less is particularly preferable. When the hydroxyl group-containing polymer has an Mw of less than 1,000, tack-free properties when a resin composition is heated and dried to form a coating film, and heat resistance of a cured coating film obtained using the resin composition are poor. May be sufficient. On the other hand, if Mw exceeds 50,000, the alkali developability of the coating film may be lowered.

<Polybasic acid anhydride>
The polybasic acid anhydride used in the present invention is particularly limited as long as it can add a carboxyl group to the side chain of the hydroxyl group-containing polymer by addition reaction with the hydroxyl group of the hydroxyl group-containing polymer. Not. For example, polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3, 6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic anhydride or maleic anhydride Dibasic acid anhydrides such as reactants; trimellitic anhydride; biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentane Tet Dianhydride, pyromellitic acid anhydride, aliphatic such as benzophenone tetracarboxylic acid dianhydride or aromatic tetrabasic acid dianhydride, and the like. These polybasic acid anhydrides may be used alone or in combination of two or more.

<Modified polymer having carboxyl group in side chain (I)>
Since the modified polymer (I) having a carboxyl group in the side chain used in the present invention has a necessary amount of carboxyl groups in the side chain while having an appropriate molecular weight, the modified polymer (I) The coating film of the resin composition containing can have favorable alkali developability.

  For the coating film of the resin composition of the present invention, the acid value of the modified polymer (I) is preferably 30 mgKOH / g or more, and 50 mgKOH / g in order to develop good alkali developability even in a weak alkaline aqueous solution. More preferably, it is 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. When the acid value of the modified polymer (I) is less than 30 mgKOH / g, the coating film may not be able to exhibit good alkali developability. Moreover, when the acid value of modified polymer (I) exceeds 150 mgKOH / g, the water resistance and moisture resistance of a cured coating film may deteriorate.

<Compound that reacts with thiol group>
If the compound which reacts with the thiol group used by this invention reacts with the thiol group which the thiol compound which did not act as a chain transfer agent among the thiol compounds used when preparing a hydroxyl group containing polymer, it reacts. There is no particular limitation. Thereby, thiol compound activity can be deactivated. For example, examples of the compound that reacts with the thiol group include an epoxy compound, a vinyl ether compound, and a vinyl thioether compound. These may be used alone or in appropriate combination of two or more. A compound having both a functional group that reacts with a thiol group and an ethylenically unsaturated double bond in one molecule is compound A (described later) used when the modified polymer (I) is converted to the modified polymer (II). This is preferable because it can be Moreover, the reaction product obtained by using the compound that reacts with the thiol group has an ethylenically unsaturated double bond, and can be polymerized with the modified polymer (II).

  The epoxy compound is not particularly limited as long as it is a compound having an epoxy group capable of reacting with a thiol group. For example, a compound having one epoxy group in one molecule such as glycidyl (meth) acrylate, allyl glycidyl ether, glycidol, bisphenol type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, And known epoxy resins such as cresol novolac type epoxy resins, homopolymers and copolymers of monomers having a glycidyl group such as glycidyl (meth) acrylate, and the like. For the above-mentioned reasons, glycidyl (meth) acrylate, allyl glycidyl ether or the like having an ethylenically unsaturated double bond is preferred.

  The vinyl ether compound is not particularly limited as long as it is a compound having a double bond capable of reacting with a thiol group. For example, aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; 2- (vinyloxyethoxy) ethyl (meth) acrylate , 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, and the like.

  The vinyl thioether compound is not particularly limited as long as it is a compound having a double bond capable of reacting with a thiol group. For example, the compound formed by substituting the oxygen atom of said vinyl ether compound with a sulfur atom is mentioned. That is, aliphatic vinyl thioether corresponding to the above vinyl ether compound; cycloalkyl vinyl thioether and the like can be mentioned.

<Reaction product of thiol compound and compound that reacts with thiol group>
The reaction product of the thiol compound and the compound that reacts with the thiol group contained in the resin composition of the present invention is a by-product that is produced as a by-product when the modified polymer (I) used in the present invention is obtained.

  The reaction product contained in the resin composition of the present invention contains an S atom derived from a thiol residue, and usually has a molecular weight obtained by adding the molecular weights of a thiol compound and a compound that reacts with a thiol group. . When a compound having a plurality of functional groups that react with thiol groups is used as the compound that reacts with thiol groups, the reaction product contained in the resin composition of the present invention has a molecular weight of the compound that reacts with thiol groups. In addition, there is a possibility that the molecular weight is the sum of the molecular weights of the thiol compounds corresponding to the number of functional groups that react with the thiol group.

  In addition, when obtaining a cured coating film using the resin composition of this invention, the said reaction product may be removed.

<N-substituted maleimide>
The hydroxyl group-containing polymer used in the present invention preferably contains N-substituted maleimide as an essential component in addition to the hydroxyl group-containing monomer as a monomer component. With this configuration, a resin composition having excellent heat resistance after curing can be obtained.

  Examples of the N-substituted maleimide used in the present invention include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tri Bromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2, 4,6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) Maleimide, N-(1-hydroxyphenyl) maleimide and the like. These N-substituted maleimides may be used alone or in combination of two or more. Among these N-substituted maleimides, N-phenylmaleimide and N- (2- (2-)) have a large effect of improving heat resistance, good copolymerizability with a hydroxyl group-containing monomer and the like, and are easily available. Methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-laurylmaleimide, N-cyclohexylmaleimide and the like are preferable, N-phenylmaleimide and N-cyclohexylmaleimide are more preferable, and N-phenylmaleimide is most preferable. .

  The content of the N-substituted maleimide is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and 80 mol% or less when the hydroxyl group-containing polymer is 100 mol%. Preferably, 70 mol% or less is more preferable, and 60 mol% or less is more preferable. When the content of the N-substituted maleimide is less than 5 mol%, sufficient heat resistance cannot be imparted to the cured coating film of the resin composition of the present invention. On the other hand, if the content of the N-substituted maleimide exceeds 80 mol%, the content of the hydroxyl group-containing monomer is relatively reduced, so the amount of carboxyl groups introduced using the polybasic acid anhydride is It may be insufficient to develop alkali developability in the coating film of the resin composition.

<Other monomers>
The hydroxyl group-containing polymer used in the present invention may comprise a monomer component other than the above hydroxyl group-containing monomer and N-substituted maleimide.

  The other monomer is not particularly limited as long as it is copolymerizable with a hydroxyl group-containing monomer or N-substituted maleimide. For example, styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene Aromatic vinyl monomers such as vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic monomers such as butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-dodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate; n-propyl vinyl ether, isopropyl Vinyl ether, n-butyl vinyl ether, isobutyl vinyl Alkyl ethers such as ruether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, and corresponding alkyl vinyl (thio) ethers; monomers containing acid anhydride groups such as maleic anhydride or alcohols, amines, Examples include monomers obtained by ring-opening modification of acid anhydride groups with water or the like; N-vinyl monomers such as N-vinylpyrrolidone and N-vinyloxazolidone. These other monomers may be used alone or in combination of two or more.

  The content of the other monomer is not particularly limited, and the content of the hydroxyl group-containing monomer, N-substituted maleimide, and other monomer when the hydroxyl group-containing polymer is 100 mol%. What is necessary is just to adjust suitably so that the sum of quantity may be 100 mol%.

(Photosensitive resin composition)
As mentioned above, although the resin composition of this invention was demonstrated, below, the photosensitive resin composition comprised including the said resin composition is demonstrated.

<Polymerizable compound having an ethylenically unsaturated double bond>
The photosensitive resin composition of this invention may be comprised further including the polymeric compound which has an ethylenically unsaturated double bond in the said resin composition. With such a configuration, the photosensitive resin composition of the present invention has not only alkali developability but also photopolymerizability, so that it is preferably used for an alkali development type photosensitive resin composition for image formation. it can.

  The polymerizable compound having an ethylenically unsaturated double bond contained in the photosensitive resin composition of the present invention is not particularly limited as long as photopolymerizability can be imparted to the resin composition of the present invention. Moreover, it is not limited about the aspect of a polymeric compound, Either of polymeric resin and a polymerizable monomer may be sufficient.

  Examples of the polymerizable resin having an ethylenically unsaturated double bond used in the present invention include unsaturated polyester, epoxy acrylate, urethane acrylate, and polyester acrylate.

  In particular, epoxy acrylate has good photopolymerizability and is effective in improving the properties of a cured product obtained using the photosensitive resin composition of the present invention. Moreover, it is excellent in blendability with the modified polymer (I). As the epoxy acrylate, a reaction product of a known epoxy resin having two or more epoxy groups in one molecule and an unsaturated monobasic acid (such as (meth) acrylic acid) can be used as it is. A preferable epoxy resin is an epoxy resin having three or more epoxy groups in one molecule, more preferably a novolac type epoxy resin, and still more preferably a novolac type epoxy resin having a softening point of 75 ° C. or higher. Thereby, tack-free property at the time of heat-drying the photosensitive resin composition of this invention and forming a coating film becomes favorable. As the epoxy acrylate, a carboxyl group-containing epoxy acrylate obtained by addition reaction of the above-mentioned polybasic acid anhydride to the hydroxyl group of the epoxy acrylate can also be used. Thereby, the coating film of the photosensitive resin composition of this invention can maintain high level alkali developability. The reaction between the epoxy acrylate and the polybasic acid anhydride can be performed by the same method (described later) as the reaction between the hydroxyl group-containing polymer and the polybasic acid anhydride.

  When a polymerizable resin is used as the polymerizable compound, the content of the polymerizable resin is set to a modified weight in order to effectively exhibit the characteristics derived from the modified polymer (I) or the modified polymer (II) (described later). When the total amount of the solid content of the polymer (I) or the modified polymer (II) and the polymerizable resin solid is 100% by mass, the content of the polymerizable resin is preferably 80% by mass or less, and 70% by mass. More preferably, it is more preferably 60% by mass or less.

  The polymerizable monomer having an ethylenically unsaturated double bond used in the present invention is composed of a monofunctional (one ethylenically unsaturated double bond) monomer and a polyfunctional monomer (ethylenically unsaturated double bond). Any of two or more bonds) can be used. The polymerizable monomer is involved in photopolymerization, and can improve the properties of the cured product obtained using the photosensitive resin composition, and can further adjust the viscosity of the photosensitive resin composition.

  As the monofunctional monomer, the above-mentioned hydroxyl group-containing monomer used in preparing the hydroxyl group-containing polymer of the present invention, or N- which may be used in preparing such a hydroxyl group-containing polymer. Substituted maleimides and other monomers are mentioned.

  Specific examples of the polyfunctional monomer include aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tri Such as methylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acryloyloxyethyl] triazine, etc. ) Acrylic monomer; 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxy) (meth) acrylate Toxyl) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl and other ethyl etheric unsaturated vinyl ether compounds and corresponding vinyl thioether compounds; triallyl cyanurate etc. capable of radical polymerization And a polyfunctional monomer having two or more ethylenically unsaturated double bonds.

  These polymerizable monomers are appropriately selected according to the use and required characteristics of the photosensitive resin composition, and can be used alone or in combination of two or more.

  When a polymerizable monomer is used as the polymerizable compound, the content of the polymerizable monomer is 100 mass of the total amount of the modified polymer (I) or the modified polymer (II) solid content and the polymerizable resin solid content. 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 500 parts by mass or less is preferable, and 100 parts by mass or less is more preferable.

<Compound having a functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond in one molecule (compound A)>
In the photosensitive resin composition of the present invention, the modified polymer (I) is one of the hydroxyl groups possessed by the modified polymer (I) and / or one of the carboxyl groups possessed by the modified polymer (I). In part, a functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group and a compound (compound A) having an ethylenically unsaturated double bond in one molecule reacted, and an ethylenically unsaturated double bond in the side chain. Further, it is preferably a modified polymer (II). With such a configuration, the modified polymer (II) used in the present invention has at least a carboxyl group and an ethylenically unsaturated double bond in one molecule, so that the modified polymer (II) alone is an alkali developing type. The photosensitive resin composition for image formation can be obtained.

  Examples of the functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group in Compound A include an isocyanate group, a vinyl ether group, an epoxy group, an oxazolinyl group, an aziridinyl group, and an oxetanyl group. These functional groups may be contained alone in Compound A or in combination of two or more kinds in Compound A.

  Examples of the compound A used in the present invention include isocyanate ethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isopropenyl-2-oxazoline. , N- (meth) acryloylaziridine and the like. These compounds A may be used alone or in combination of two or more.

<Modified polymer (II) further having an ethylenically unsaturated double bond in the side chain>
The acid value of the modified polymer (II) used in the present invention is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less. When the acid value of the modified polymer (II) is less than 30 mgKOH / g, the coating film may not be able to exhibit good alkali developability. Moreover, when the acid value of modified polymer (II) exceeds 150 mgKOH / g, the water resistance and moisture resistance of a cured coating film may deteriorate.

  The modified polymer (II) used in the present invention may be prepared by consuming the carboxyl group of the modified polymer (I). Therefore, when it is planned to use the compound A having a functional group that undergoes an addition reaction with the carboxyl group of the modified polymer (I), the acid value of the modified polymer (I) is previously in the above range (30 mgKOH / g or more and 150 mgKOH / g or less). Specifically, the acid value of the modified polymer (I) is preferably 35 mgKOH / g or more and 200 mgKOH / g or less.

  The content of the ethylenically unsaturated double bond of the modified polymer (II) used in the present invention is preferably 0.005 mol or more, more preferably 0.01 mol or more per 100 parts by mass of the modified polymer (II). 0.02 mol or more is more preferable, 0.3 mol or less is preferable, 0.1 mol or less is more preferable, and 0.05 mol or less is more preferable. When the content of the ethylenically unsaturated double bond is less than 0.005 mol, the modified polymer (II) may not exhibit sufficient photopolymerizability. In addition, when the content of ethylenically unsaturated double bonds exceeds 0.3 mol, the amount of carboxyl groups of the modified polymer (II) may be relatively decreased, and the modified polymer (II) There is a possibility that the coating film of the photosensitive resin composition of the present invention containing sufficient alkaline developability cannot be exhibited.

<Compound having a functional group that reacts with two or more carboxyl groups in one molecule (compound B)>
The photosensitive resin composition of the present invention may further comprise a compound (compound B) having a functional group that reacts with two or more carboxyl groups in one molecule. With this configuration, the photosensitive resin composition of the present invention is cured not only by light but also by heat. Therefore, if the photosensitive resin composition of the present invention is cured using both light and heat, a stronger cured coating film can be obtained. In addition, since compound B also undergoes an addition reaction with the carboxyl group of modified polymer (I) or modified polymer (II), the photosensitive resin composition of the present invention is irradiated with light and then subjected to alkali development, followed by further heat treatment. By doing this, the degree of crosslinking can be increased while consuming the carboxyl groups in the cured coating film. As a result, it is possible to further improve physical properties such as durability, water resistance, and moisture resistance of the obtained cured coating film.

  Examples of the compound B used in the present invention include an epoxy compound, an oxazoline compound, and an oxetane compound. Specifically, examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and triglycidyl isosialate. Examples of the oxazoline compound include 1,3-phenylenebisoxazoline. Examples of the oxetane compound include 1,4-bis [3- (3-ethyloxetanyl) methoxy] benzene.

  The content of Compound B is 5 parts by weight based on a total of 100 parts by mass of the total content of the solid content of the modified polymer (I) or the modified polymer (II) and the polymerizable compound solid content having an ethylenically unsaturated double bond. It is preferably at least 10 parts by mass, more preferably at least 10 parts by mass, preferably at most 70 parts by mass, more preferably at most 50 parts by mass.

  When the photosensitive resin composition of this invention contains the compound B, hardening | curing agents, such as a dicyandiamide and an imidazole compound, may further be contained.

<Other components>
The photosensitive resin composition of the present invention may further include other constituent components in addition to the above constituent components.

  For example, a solvent is mentioned as another structural component. Thereby, workability | operativity etc. at the time of apply | coating the photosensitive resin composition to a base material improve.

  The solvent used in the present invention is not particularly limited as long as the solid content of the photosensitive resin composition can be dissolved and there is no fear of modifying each component. For example, hydrocarbons such as toluene and xylene; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid (di) methyl, succinic acid (di) methyl, adipic acid (di) methyl, methyl acetate Esters such as ethyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, methyl-t-butyl ether, (di ) Ethers such as ethylene glycol dimethyl ether and (di) ethylene glycol monoethyl ether; amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide. It is. These solvents may be used alone or in combination of two or more.

  The content of the solvent is not particularly limited, and an appropriate amount may be used so that the photosensitive resin composition has an optimum viscosity during the coating operation.

  The photosensitive resin composition of the present invention preferably comprises a photopolymerization initiator. Such a configuration promotes the photopolymerization reaction of the photopolymerizable compound (for example, a polymerizable compound having an ethylenically unsaturated double bond or a modified polymer (II)) contained in the photosensitive resin composition of the present invention. Can do. Therefore, the photosensitive resin composition of the present invention can be subjected to fine processing and image formation by photolithography.

  The photopolymerization initiator used in the present invention is not particularly limited. For example, benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal Benzophenones, such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones Can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

  Content of a photoinitiator is 0.5 with respect to 100 mass parts in total of the solid content of modified polymer (I) or modified polymer (II), and the polymeric compound which has an ethylenically unsaturated double bond. The amount is preferably at least part by mass, and preferably at most 30 parts by mass. When the content of the photopolymerization initiator is less than 0.5 parts by mass, it is necessary to increase the light irradiation time when photopolymerizing the photosensitive resin composition, or polymerization is difficult to occur even if light irradiation is performed. As a result, an appropriate surface hardness may not be obtained. In addition, even if content of a photoinitiator exceeds 30 mass parts, there is no merit to use in large quantities.

  The photosensitive resin composition of the present invention may further include a filler such as talc, clay, barium sulfate, a coloring pigment, an antifoaming agent, a coupling agent, a leveling agent, a sensitizer, a release agent, if necessary. Known additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors and thickeners may be included.

<Application>
The photosensitive resin composition of the present invention can achieve both sensitivity during exposure and alkali developability. More specifically, the photosensitive resin composition of the present invention is applied onto a substrate, heat-dried to form a coating film, and then a pattern forming film is attached to the coating film with a development time of 30 to 300 seconds. It is exposed to light to obtain a cured coating film, and the unexposed part (uncured part) can be dissolved and removed using an aqueous sodium carbonate solution at a liquid temperature of 30 ± 5 ° C. at 0.5 to 5% by mass. Can do. Moreover, the hardened | cured material which is excellent in heat resistance, but does not express a brittleness can be given. For this reason, the photosensitive resin composition of the present invention is, for example, a solder resist for printed wiring boards, an etching resist, an electroless plating resist, or a build-up method printed wiring board as an alkali-developable photosensitive resin composition for image formation. It can be used suitably for various uses such as an insulating layer, a liquid crystal display plate production, printing plate making and the like.

  Specific examples of alkalis that can be used for alkali development of the photosensitive resin composition of the present invention include, in addition to sodium carbonate, alkali metal compounds such as potassium carbonate, sodium hydroxide and potassium hydroxide; Alkaline earth metal compounds such as calcium; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylamino Water-soluble organic amines such as ethyl methacrylate and polyethyleneimine can be mentioned. These alkalis may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention can be used in the form of a dry film by coating and drying in advance on a base film such as polyethylene terephthalate in addition to being applied directly to a substrate in liquid form. In this case, a dry film may be laminated on a substrate, and the base film may be peeled off before or after exposure.

  Further, when the photosensitive resin composition of the present invention is used for printing plate making applications, a CTP (Computer To Plate) system that has been widely used recently in the printing plate making field, that is, without using a pattern forming film during exposure. It is also possible to employ a method of drawing by scanning and exposing a laser beam directly onto the coating film using digitized data.

(Production method of resin composition)
The (photosensitive) resin composition of the present invention has been described above. Hereinafter, the method for producing the (photosensitive) resin composition of the present invention will be described in detail.

  The method for producing a resin composition of the present invention includes a step of obtaining a hydroxyl group-containing polymer by mixing and polymerizing components including a thiol compound, a hydroxyl group-containing monomer, and a polymerization initiator, A modified polymer having a carboxyl group in the side chain by further mixing a compound that reacts with a group, a polybasic acid anhydride, and a reaction catalyst of the polybasic acid anhydride and a hydroxyl group; I) is obtained.

  According to the production method of the present invention, among the thiol compounds used in the step of obtaining the hydroxyl group-containing polymer, it was not involved in the molecular weight adjustment of the hydroxyl group-containing polymer, that is, it was not bonded to the end of the polymer. A reaction catalyst that catalyzes the addition reaction of hydroxyl groups and polybasic acid anhydrides in a hydroxyl group-containing polymer after reacting a free thiol compound with a compound that reacts with a thiol group to deactivate the thiol compound in advance. Will be mixed. That is, in the production method of the present invention, the reaction catalyst between the hydroxyl group and the polybasic acid anhydride is prevented from being deactivated by the thiol compound. For this reason, the manufacturing method of this invention can perform effectively the addition reaction of the polybasic acid anhydride to the hydroxyl group containing polymer by which molecular weight was adjusted moderately.

<Step of obtaining a hydroxyl group-containing polymer>
Specific embodiments of the thiol compound and the hydroxyl group-containing monomer used in this step are as described above.

  The polymerization initiator used in this step is not particularly limited as long as it initiates radical polymerization of a monomer component containing a hydroxyl group-containing monomer. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 Azo compounds such as 2,2'-azobis (2-methylisobutyronitrile); lauroyl peroxide, benzoyl peroxide, t-butylperoxyneodecanate, t-butylperoxypivalate, t-butylperoxy Examples thereof include organic peroxides such as 2-ethylhexanoate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide. These polymerization initiators may be used alone or in combination of two or more.

  The mixing amount of the polymerization initiator is preferably 0.01 parts by mass or more with respect to 100 parts by mass in total of the monomer components including the hydroxy-containing monomer for obtaining the hydroxyl group-containing polymer, and 0.1 mass by mass. Part or more is more preferable, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.

  The mixing amount of the thiol compound may be appropriately adjusted so as to obtain a hydroxyl group-containing polymer having a desired molecular weight, and is not particularly limited. 0.001 mol or more is preferable with respect to 1 mol of monomer components used, and 1.0 mol or less is preferable.

  In this step, the polymerization method of the monomer component containing the hydroxyl group-containing monomer can employ a conventionally known polymerization method such as a solution polymerization method or a bulk polymerization method, but the temperature control during the polymerization reaction can be performed. The solution polymerization method is preferable from the viewpoint of ease.

  The solvent used when this step is carried out by a solution polymerization method is particularly limited as long as it does not inhibit the polymerization of monomer components such as hydroxyl group-containing monomers or alter the monomer components. Not. Specifically, the above-mentioned solvent used for improving the workability and the like of the photosensitive resin composition of the present invention can be mentioned.

  The method of adding each component such as a thiol compound, a hydroxyl group-containing monomer, and a polymerization initiator when this step is performed by a solution polymerization method is not particularly limited, and all the components are temporarily contained in a solvent. A method of charging and polymerizing, a method of continuously adding or sequentially adding the remaining components to a reaction vessel in which a solvent and a part of the components have been previously charged, and a method of performing polymerization can be employed.

  This step may be performed under normal pressure or pressurized conditions. Moreover, the temperature at the time of a polymerization reaction can be suitably adjusted with the kind and composition ratio of monomer components, such as a hydroxyl group containing monomer to be used, and the kind of solvent to be used. The temperature during the polymerization reaction is usually preferably 20 ° C. or higher, more preferably 30 ° C. or higher, preferably 150 ° C. or lower, and more preferably 120 ° C. or lower.

  When performing this step by a solution polymerization method, it is preferable to set the amount of the solvent and each component so that the final solid content concentration of the solution containing the hydroxyl group-containing polymer is 10% by mass or more, and 20% by mass. More preferably, it is more preferably 30% by mass or more, further preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less. When the final solid content concentration is less than 10% by mass, the productivity of the hydroxyl group-containing polymer is lowered. On the other hand, when the final solid content concentration exceeds 70% by mass, the viscosity of the polymerization solution may increase and the polymerization conversion rate may not increase.

  When this step is performed by a solution polymerization method, a solution containing a hydroxyl group-containing polymer and a free thiol compound is obtained.

<The process of mixing the compound which reacts with a thiol group>
The specific mode of the compound that reacts with the thiol group used in this step is as described above.

  The mixing amount of the compound that reacts with the thiol group is preferably 0.5 mol or more, more preferably 0.8 mol or more, more preferably 5 mol or less with respect to 1 mol of the thiol compound used in the step of obtaining the hydroxyl group-containing polymer. Preferably, 3 mol or less is more preferable. When the amount of the compound that reacts with the thiol group is less than 0.5 mol, the compound that reacts with the thiol group reacts with the thiol compound, that is, the thiol compound cannot be completely deactivated. There is. Moreover, even if the usage-amount of the compound which reacts with a thiol group exceeds 5 mol, there is no merit as much as the left.

  When the thiol compound remains in the production method of the present invention, the remaining thiol compound deactivates the reaction catalyst involved in the addition reaction between the hydroxyl group of the hydroxyl group-containing polymer and the polybasic acid anhydride. Thus, not only the addition reaction is inhibited, but also the storage stability of the resulting resin composition may be lowered. Furthermore, it takes a long time to cure the resin composition, and the average molecular weight of the resulting cured product may not increase.

  The method for adding the compound that reacts with the thiol group in this step is not particularly limited, and for example, a component containing a thiol compound, a hydroxyl group-containing monomer, and a polymerization initiator is mixed and polymerized. The method of adding the compound which reacts with a thiol group to the reaction solution containing the hydroxyl group containing polymer obtained by this, the method of adding the said reaction solution to the compound which reacts with a thiol group, etc. are mentioned. Thereby, the mixture solution containing the hydroxyl group-containing polymer, the reaction product of the compound that reacts with the thiol group and the thiol compound is obtained.

  The treatment temperature in performing this step is preferably room temperature or higher, more preferably 50 ° C. or higher, preferably 150 ° C. or lower, and more preferably 120 ° C. or lower. Other treatment conditions such as treatment time may be determined according to the type of thiol compound used to prepare the hydroxyl group-containing polymer or the compound that reacts with the thiol group, and are not particularly limited. Absent.

  This step may be performed by further mixing a catalyst such as a Lewis acid, an amine salt, a tertiary amine, a quaternary ammonium salt, a phosphonium salt, or a metal salt. Thereby, reaction with the compound which reacts with the thiol group which a thiol compound has, and a thiol group can be accelerated | stimulated.

<Step of obtaining modified polymer (I) having carboxyl group in side chain>
The specific embodiment of the polybasic acid anhydride used in this step is as described above.

  The mixing amount of the polybasic acid anhydride is preferably such that the acid anhydride group in the polybasic acid anhydride is 0.1 mol or more per one chemical equivalent of hydroxyl group in the hydroxyl group-containing polymer. More preferably, it is 2 mol or more, preferably 1.1 mol or less, and more preferably 0.9 mol or less.

  The reaction catalyst used in this step is not particularly limited as long as it promotes the reaction between the hydroxyl group of the hydroxyl group-containing polymer and the polybasic anhydride. For example, tertiary amine, quaternary ammonium One or more kinds of reaction catalysts selected from the group consisting of a salt, an imidazole compound, a phosphorus compound, a carboxylic acid metal salt, and an inorganic metal salt are included. Examples of the tertiary amine include triethylamine. Examples of the quaternary ammonium salt include triethylbenzylammonium chloride. Examples of the imidazole compound include 2-ethyl-4-methylimidazole. Examples of the phosphorus compound include triphenylphosphine and tetraphenylphosphonium bromide. Examples of the carboxylic acid metal salt include lithium acetate. Examples of the inorganic metal salt include lithium carbonate.

  The mixing amount of the reaction catalyst is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, with respect to 100 parts by mass of the total amount of the hydroxyl group-containing polymer and the polybasic acid anhydride, and 1 part by mass or less. Is preferable, and 0.5 mass part or less is more preferable. When the mixing amount of the reaction catalyst is less than 0.01 part by mass, the addition reaction of the polybasic acid anhydride to the hydroxyl group of the hydroxyl group-containing polymer may not proceed. Moreover, when the mixing amount of a reaction catalyst exceeds 1 mass part, the coating film of the photosensitive resin composition obtained through the manufacturing method of this invention cannot be alkali-developed. That is, the manufacturing method of the photosensitive resin composition of this invention may include the process of mixing the compound B so that it may mention later. Therefore, when an excessive amount of reaction catalyst is used in this step, the photosensitive resin composition of the present invention contains a modified polymer (I) or a modified polymer (II) (described later), compound B, and an excess amount. And a reaction catalyst. On the other hand, the reaction catalyst used in this step promotes the reaction (crosslinking) between the compound B and the modified polymer (I) or the modified polymer (II). Therefore, when the photosensitive resin composition is pre-dried before exposure, the photosensitive resin composition is cured. As a result, even if the photosensitive resin composition is subsequently exposed, the unexposed portion is cured, so that alkali development cannot be performed.

  The addition method of the polybasic acid anhydride and the reaction catalyst in this step is not particularly limited. For example, the reaction with a thiol compound and a thiol group obtained through a step of mixing a compound that reacts with a thiol group. And a method of adding a polybasic acid anhydride and a reaction catalyst to a mixture solution containing a reaction product with a compound to be synthesized and a hydroxyl group-containing polymer.

  The reaction temperature in this step is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, preferably 150 ° C. or lower, and preferably 120 ° C. or lower. Moreover, reaction time is not specifically limited, What is necessary is just to determine according to the component etc. which were used for preparing a hydroxyl-group containing polymer, a polybasic acid anhydride, and the kind of catalyst.

The progress of this step can be confirmed by infrared absorption spectrum (IR) analysis of the reaction solution and whether or not absorption near 1850 cm ⁻¹ derived from the acid anhydride group has disappeared.

<Mixture of N-substituted maleimide, etc.>
The method for producing a resin composition of the present invention is performed by further mixing and polymerizing an N-substituted maleimide in addition to a hydroxyl group-containing monomer as a monomer component in the step of obtaining a hydroxyl group-containing polymer. It is preferable. Moreover, you may mix another monomer.

  Specific embodiments of the N-substituted maleimide and other monomers used in this step are as described above.

  The mixing amount of the N-substituted maleimide and other monomers is appropriately determined so that the content of the N-substituted maleimide and other monomers in the hydroxyl group-containing polymer is within the above-described preferable range. Adjust it.

  In addition, even if it is a case where this process is included, the special change is not required for the reaction conditions of the process of obtaining a hydroxyl group containing polymer.

(Method for producing photosensitive resin composition)
As mentioned above, although the manufacturing method of the resin composition of this invention was demonstrated, it can be set as the manufacturing method of the photosensitive resin composition including the following process further.

<The process of mixing the polymeric compound which has an ethylenically unsaturated double bond>
The manufacturing method of the photosensitive resin composition of this invention may be comprised including the process of further mixing the polymeric compound which has an ethylenically unsaturated double bond in the manufacturing process of the said resin composition.

  Specific embodiments of the polymerizable compound having an ethylenically unsaturated double bond used in this step are as described above.

  The mixing amount of the polymerizable compound having an ethylenically unsaturated double bond is based on the total amount of the solid content of the modified polymer (I) or the modified polymer (II) (described later) and the solid content of the polymerizable compound. What is necessary is just to adjust suitably so that content of a polymeric compound may become in the above-mentioned preferable range.

  This step may be performed at any stage of the method for producing the photosensitive resin composition of the present invention, but when the polymerizable compound having an ethylenically unsaturated double bond is used to prepare a hydroxyl group-containing polymer. In order to prevent consumption as a monomer component, it is preferably performed after the step of obtaining a hydroxyl group-containing polymer.

<Process for making modified polymer (II) further having ethylenically unsaturated double bond in side chain>
In the method for producing a photosensitive resin composition of the present invention, the modified polymer (I) has a functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond in one molecule. The method may further comprise a step of further mixing the compound (Compound A) to obtain a modified polymer (II) further having an ethylenically unsaturated double bond in the side chain.

  Specific embodiments of Compound A used in this step are as described above.

  The amount of compound A used in this step is such that the acid value of the modified polymer (II) is within the above range, and the content of the ethylenically unsaturated double bond of the modified polymer (II) is within the above range. What is necessary is just to adjust suitably so that it may become.

  This step may be carried out at any stage of the method for producing the photosensitive resin composition of the present invention as long as it is after the step of obtaining the hydroxyl group-containing polymer. For example, the step of obtaining the hydroxyl group-containing polymer It can be performed after, before or after the step of obtaining the modified polymer (I), or simultaneously with the step of obtaining the modified polymer (I).

  The reaction conditions in this step are not particularly limited, and the catalyst, reaction temperature, etc. may be appropriately adjusted using known techniques used in the reaction of the functional group of compound A with a hydroxyl group or a carboxyl group. That's fine.

<The process of mixing the compound (compound B) which has a functional group which reacts with two or more carboxyl groups in one molecule>
The method for producing a photosensitive resin composition of the present invention includes a step of mixing a compound (compound B) having a functional group that reacts with two or more carboxyl groups in one molecule in the method for producing the resin composition. Can be configured.

  Specific embodiments of Compound B used in this step are as described above.

  The mixing amount of Compound B is within the range in which the content of Compound B is preferably the above-mentioned amount with respect to the total amount of the solid content of the modified polymer (I) or the modified polymer (II) and the solid content of the polymerizable compound. It may be adjusted as appropriate.

  In this step, the photosensitive resin composition obtained through the production method of the present invention is irradiated with light and then subjected to alkali development, so long as compound B can remain almost unreacted in the cured product. It may be carried out at any stage of the production method.

<Other processes>
As mentioned above, although the manufacturing method of the photosensitive resin composition of this invention was demonstrated, the manufacturing method of this invention is not limited to the said aspect, You may be comprised including the following aspects.

  For example, the production method of the present invention includes a solvent, a photopolymerization initiator, a filler such as talc, clay, barium sulfate, a coloring pigment, an antifoaming agent, a coupling agent, a leveling agent, a sensitizer, and a release agent. And a step of mixing known additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a polymerization inhibitor, and a thickener.

(Resin composition produced by the above production method and photosensitive resin composition)
The resin composition and the photosensitive resin composition of the present invention can be specified by the method for producing the resin composition and the method for producing the photosensitive resin composition.

  The (photosensitive) resin composition of the present invention and the method for producing the same have been described above. However, the present invention includes various improvements, modifications, and variations based on the knowledge of those skilled in the art without departing from the spirit of the present invention. Can be implemented.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the present invention are within the technical scope of the present invention. Is included. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

(Synthesis Example 1)
Synthesis of modified polymer (II-1) further having an ethylenically unsaturated double bond in the side chain <Step of obtaining hydroxyl group-containing polymer>
A vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel was charged with 125 parts of diethylene glycol monoethyl ether acetate as a solvent, and the inside of the vessel was purged with nitrogen for 10 minutes. Heated to 90 ° C.

  Two dropping funnels were prepared. One of them was 151 parts of 2-hydroxypropyl methacrylate as a hydroxyl group-containing monomer, 82 parts of 2-ethylhexyl methacrylate as another monomer, and N-cyclohexylmaleimide as an N-substituted maleimide. 112 parts, 340 parts of diethylene glycol monoethyl ether acetate as a solvent and 8.6 parts of perbutyl (registered trademark) O (manufactured by NOF Corporation) as a polymerization initiator were charged, and a solution (A liquid) was charged into the dropping funnel. Was purged with nitrogen for 5 minutes. In addition, a solution (liquid B) obtained by mixing 5.2 parts of n-dodecyl mercaptan as a thiol compound (chain transfer agent) and 20 parts of diethylene glycol monoethyl ether acetate as a solvent was added to the other one, and a dropping funnel The inside was replaced with nitrogen for 5 minutes.

  After carrying out nitrogen substitution of the container and the dropping funnel, the solutions (A liquid and B liquid) in the two dropping funnels were dropped over 3 hours while maintaining the temperature in the container at 90 ° C. and continuing stirring. . After completion of the dropping, 1.7 parts of perbutyl (registered trademark) O was added and maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. and polymerization was continued for 2 hours to obtain a hydroxyl group-containing polymer.

<The process of mixing the compound which reacts with a thiol group>
Subsequently, 3.7 parts of glycidyl methacrylate as a compound that reacts with a thiol group and 0.2 part of methyl hydroquinone as a polymerization inhibitor are added to the container, and a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%) Is added. The mixture was kept at 90 ° C. for 1 hour with stirring to deactivate the thiol group.

<Step of obtaining modified polymer (I-1) having carboxyl group in side chain>
Subsequently, 110 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride and 1 part of benzyltriethylammonium chloride as a catalyst were placed in a container and stirred in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The mixture was reacted at 110 ° C. for 3 hours to obtain a modified polymer (I-1) having a carboxyl group in the side chain.

<The process made into the modified polymer (II-1) which further has an ethylenically unsaturated double bond in a side chain>
Subsequently, 26.3 parts of glycidyl methacrylate as compound A and 0.3 part of methyl hydroquinone as a polymerization inhibitor are added to the container, and the mixture is stirred in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The reaction was performed at 115 ° C. for 5 hours. As a result, a modified polymer (II) having an acid value of 61 mgKOH / g, a polystyrene-reduced weight average molecular weight (Mw) of 19000 by gel permeation chromatography (GPC), and further having an ethylenically unsaturated double bond in the side chain (II A diethylene glycol monoethyl ether acetate solution having 50.2% of -1) was obtained.

Measurement conditions by GPC are as follows.
Measuring device HLC-8020 (manufactured by Tosoh Corporation)
Column TSKgel G4000H x 1, TSKgel G3000H x 2, TSKgel G2000H x 1 connected in series (all manufactured by Tosoh Corporation)
Eluent Tetrahydrofuran eluent flow rate 1ml / min detector RI

(Synthesis Example 2)
Synthesis of modified polymer (II-2) having ethylenically unsaturated double bond in side chain In Synthesis Example 1, 10.4 parts of n-dodecyl mercaptan used as a thiol compound (chain transfer agent), and a thiol group The reaction was conducted in the same manner as in Synthesis Example 1 except that 7.4 parts of glycidyl methacrylate used as the reacting compound and 22.6 parts of glycidyl methacrylate used in the step of making the modified polymer (II-1) were used. Diethylene glycol having an acid value of 62 mg KOH / g, a polystyrene-reduced weight average molecular weight (Mw) of 10,000 by GPC and 50.5% of a modified polymer (II-2) having an ethylenically unsaturated double bond in the side chain A monoethyl ether acetate solution was obtained.

(Comparative Synthesis Example 1)
Synthesis of modified polymer (II'-1) further having an ethylenically unsaturated double bond in the side chain (no thiol compound (chain transfer agent) used)
<Step of obtaining a hydroxyl group-containing monomer>
Using the same apparatus as in Synthesis Example 1, 125 parts of diethylene glycol monoethyl ether acetate was charged as a solvent, the inside of the container was purged with nitrogen for 10 minutes, and then heated until the internal temperature reached 90 ° C. with stirring.

  In a dropping funnel, 151 parts of 2-hydroxypropyl methacrylate as a hydroxyl group-containing monomer, 82 parts of 2-ethylhexyl methacrylate as another monomer, 112 parts of N-cyclohexylmaleimide as an N-substituted maleimide, and diethylene glycol monoethyl ether as a solvent A solution obtained by mixing 360 parts of acetate and 8.6 parts of Perbutyl (registered trademark) O as a polymerization initiator was charged, and the inside of the dropping funnel was purged with nitrogen for 5 minutes.

  After carrying out nitrogen substitution of the container and the dropping funnel, the solution in the dropping funnel was dropped over 3 hours while maintaining the temperature in the container at 90 ° C. and continuing stirring. After completion of the dropping, 1.7 parts of perbutyl (registered trademark) O was added and maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. and polymerization was continued for 2 hours to obtain a hydroxyl group-containing polymer.

<Step of obtaining modified polymer (I′-1) having carboxyl group in side chain>
Subsequently, 110 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride and 1 part of benzyltriethylammonium chloride as a catalyst are charged into a container and stirred under a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The reaction was carried out at 110 ° C. for 3 hours to obtain a modified polymer (I′-1) having a carboxyl group in the side chain.

<The process made into the modified polymer (II'-1) which further has an ethylenically unsaturated double bond in a side chain>
Subsequently, 30 parts of glycidyl methacrylate as compound A and 0.5 part of methylhydroquinone as a polymerization inhibitor were added to the container, and the mixture was stirred at 115 ° C. in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The reaction was allowed for 5 hours. As a result, the modified polymer (II′-1) having an acid value of 61 mg KOH / g, a weight-average molecular weight (Mw) in terms of polystyrene by GPC of 48000, and further having an ethylenically unsaturated double bond in the side chain is 50. A diethylene glycol monoethyl ether acetate solution having 0% was obtained.

(Comparative Synthesis Example 2)
Synthesis of modified polymer (II'-2) having an ethylenically unsaturated double bond in the side chain (no thiol compound (chain transfer agent) used)
<Step of obtaining a hydroxyl group-containing monomer>
Using the same apparatus as in Synthesis Example 1, 145 parts of diethylene glycol monoethyl ether acetate was charged as a solvent, the inside of the container was purged with nitrogen for 10 minutes, and then heated until the internal temperature reached 90 ° C. with stirring.

  In a dropping funnel, 186 parts of 2-hydroxypropyl methacrylate as a monomer containing a hydroxyl group, 43 parts of 2-ethylhexyl methacrylate as another monomer, 116 parts of N-cyclohexylmaleimide as an N-substituted maleimide, and diethylene glycol monoethyl ether as a solvent A solution obtained by mixing 421 parts of acetate and 8.6 parts of Perbutyl (registered trademark) O as a polymerization initiator was charged, and the inside of the dropping funnel was purged with nitrogen for 5 minutes.

  After carrying out nitrogen substitution of the container and the dropping funnel, the solution in the dropping funnel was dropped over 3 hours while maintaining the temperature in the container at 90 ° C. and continuing stirring. After completion of the dropping, 1.7 parts of perbutyl (registered trademark) O was added and held at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. and polymerization was continued for 2 hours to obtain a polymer.

<Step of obtaining modified polymer (I'-2) having carboxyl group in side chain>
Subsequently, 190 parts of tetrahydrophthalic anhydride as a polybasic acid anhydride and 1.1 parts of benzyltriethylammonium chloride as a catalyst were charged in a container and stirred in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The mixture was reacted at 110 ° C. for 4 hours to obtain a modified polymer (I′-2) having a carboxyl group in the side chain.

<The process made into the modified polymer (II'-2) which further has an ethylenically unsaturated double bond in a side chain>
Subsequently, 31 parts of glycidyl methacrylate as compound A and 0.6 part of methyl hydroquinone as a polymerization inhibitor were added to the container, and the mixture was stirred at 115 ° C. in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The reaction was allowed for 5 hours. As a result, a modified polymer (II′-2) having an acid value of 105 mg KOH / g, a weight average molecular weight (Mw) in terms of polystyrene by GPC of 51,000, and further having an ethylenically unsaturated double bond in the side chain was 50. A diethylene glycol monoethyl ether acetate solution having 0% was obtained.

(Comparative Synthesis Example 3)
In Synthesis Example 1, the step of obtaining the modified polymer (I) having a carboxyl group in the side chain was performed without performing the step of mixing the compound that reacts with the thiol group. Tetrahydroanhydride, which is a polybasic acid anhydride, was performed. Phthalic acid was not consumed, and the carboxyl group introduction reaction did not proceed.

(Examples 1-4 and Comparative Examples 1-2)
Using the resin solutions obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 and 2, photosensitive resin compositions having the formulations shown in Table 1 were prepared and evaluated by the following methods. The results are shown in Table 1.

[Developability]
After apply | coating the photosensitive resin composition on a copper plate so that the film thickness after drying might be set to 50 micrometers, it heated at 80 degreeC for 30 minutes. Thereafter, the film was immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds, and the remaining degree of the coating film was visually evaluated according to the following criteria.
○: Completely developed.
X: Deposits remain.

[Photocurability]
The dried coating film obtained in the same manner as in the evaluation of developability was exposed to ² J / cm ² using an ultraviolet exposure device, and then immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 180 seconds. Photocurability was evaluated according to the degree of remaining.
○: The coating film remains completely.
X: There exists peeling in a coating film.

[Boil resistance]
The dried coating film obtained in the same manner as in the evaluation of developability was exposed to ² J / cm ² using an ultraviolet exposure device, heated at 150 ° C. for 30 minutes, and then boiled in deionized water. Soaked for 60 seconds. The state of the coating film after immersion was visually evaluated according to the following criteria.
○: No abnormality in the appearance of the coating film.
X: There exists swelling and peeling in a part of the coating film.

  From the results of Examples 1 to 4 and Comparative Examples 1 and 2, the photosensitive resin composition according to the present invention in which the molecular weight of the modified polymer (II) was appropriately adjusted is developability, photocurability, and boiling resistance. Both of these were found to be good. From the results of Comparative Examples 1 and 2, the photosensitive resin composition prepared without using a thiol compound and having a large molecular weight of the modified polymer (II) has good developability unless the acid value is increased. On the other hand, it was found that boiling resistance deteriorates when the acid value is increased. Further, from the result of Comparative Synthesis Example 3, it was found that the modified polymer (II) could not be prepared when a compound that reacts with a thiol group was not used.

  The (photosensitive) resin composition obtained in the present invention can be suitably used as an alkali development type photosensitive resin composition for image formation.

Claims (15)

A modified polymer having a carboxyl group in the side chain, wherein a polybasic acid anhydride has reacted with at least a portion of the hydroxyl groups of a hydroxyl group-containing polymer obtained using a hydroxyl group-containing monomer as an essential component in the presence of a thiol compound ( I) and
A reaction product of a compound that reacts with a thiol group and the thiol compound;
The resin composition characterized by including.   The resin composition according to claim 1, wherein the compound that reacts with the thiol group is one or more compounds selected from the group consisting of an epoxy compound, a vinyl ether compound, and a vinyl thioether compound.   The resin composition according to claim 1 or 2, wherein the hydroxyl group-containing polymer is obtained by further using N-substituted maleimide as an essential component.   A photosensitive resin composition comprising the resin composition according to any one of claims 1 to 3 and a polymerizable compound having an ethylenically unsaturated double bond.   The modified polymer (I) according to any one of claims 1 to 3, wherein at least a part of hydroxyl groups and / or a part of carboxyl groups of the modified polymer (I) are substituted with hydroxyl groups and / or A modified polymer (II) further having an ethylenically unsaturated double bond in the side chain, in which a compound having an ethylenically unsaturated double bond in one molecule reacts with a functional group that undergoes an addition reaction with a carboxyl group A photosensitive resin composition characterized by the above.   The photosensitive resin composition of Claim 4 or 5 which further contains the compound which has the functional group which reacts with a 2 or more carboxyl group in 1 molecule. A step of obtaining a hydroxyl group-containing polymer by mixing and polymerizing components including a thiol compound, a hydroxyl group-containing monomer, and a polymerization initiator;
Further mixing a compound that reacts with a thiol group;
A step of further mixing a polybasic acid anhydride and a reaction catalyst of the polybasic acid anhydride and a hydroxyl group to obtain a modified polymer (I) having a carboxyl group in a side chain, A method for producing a resin composition.   The method for producing a resin composition according to claim 7, wherein one or more compounds selected from the group consisting of an epoxy compound, a vinyl ether compound, and a vinyl thioether compound are used as the compound that reacts with the thiol group.   9. The reaction catalyst according to claim 7 or 8, wherein at least one reaction catalyst selected from the group consisting of a tertiary amine, a quaternary ammonium salt, an imidazole compound, a phosphorus compound, a carboxylic acid metal salt, and an inorganic metal salt is used as the reaction catalyst. The manufacturing method of the resin composition of description.   The method for producing a resin composition according to any one of claims 7 to 9, wherein the step of obtaining the hydroxyl group-containing polymer is carried out by further mixing and polymerizing an N-substituted maleimide.   The resin composition manufactured by the manufacturing method of any one of Claims 7 to 10.   The manufacturing method of any one of Claims 7-10 includes the process of further mixing the polymeric compound which has an ethylenically unsaturated double bond, The manufacturing method of the photosensitive resin composition characterized by the above-mentioned.   A compound having a functional group that undergoes an addition reaction with a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond in one molecule is further mixed in the production method according to any one of claims 7 to 10. A process for producing a photosensitive resin composition comprising the step of making the modified polymer (I) a modified polymer (II) further having an ethylenically unsaturated double bond in the side chain.   The manufacturing method of the photosensitive resin composition of Claim 12 or 13 including the process of further mixing the compound which has the functional group which reacts with two or more carboxyl groups in 1 molecule.   The photosensitive resin composition manufactured by the manufacturing method of any one of Claim 12 to 14.