JP5702531B2 - Method for producing photosensitive resist ink composition for production of printed wiring board, method for producing cured product, and method for producing printed wiring board - Google Patents

Description

The present invention relates to a method for producing a photosensitive resist ink composition for producing a printed wiring board comprising a photosensitive resin composition that can be suitably used as a solder resist ink, an etching resist ink, etc., and a photosensitive resist ink composition for producing a printed wiring board The present invention relates to a method for producing a cured product and a method for producing a printed wiring board.

  Conventionally, the formation of a resist such as a solder resist or an etching resist on a printed wiring board or the like has been performed by a printing method, but it is not sufficient to cope with the recent refinement of a printed wiring board and the like, so photo development Type resist ink has been used (see Patent Documents 1 and 2).

  Evaluation items for the photo-developing resist ink include finger touch, photo-curing property, developability and the like. If the finger touch is poor, there are problems in terms of work such as resist transfer failure due to sticking of the mask film and contamination of the mask film. In addition, if the photocurability is low, the workability deteriorates because a long time is required for exposure. Also, if the developability is poor, the development time becomes long and the workability is lowered, and the resist component remains in the portion that should be developed originally, so that in the case of an etching resist or the like, an etching failure occurs, and the solder resist In some cases, problems such as poor solder adhesion occur.

  For this reason, it is desirable that the performance such as finger touch, photo-curing property, developability, etc. is all good, but with conventional photo-developing resist ink, there is a trade-off relationship between finger tack, photo-curing property and developability It is in. That is, when the molecular weight of the base resin in the resist ink is increased, the touch tack after drying can be improved. However, the base resin contains more high molecular weight components than the desired molecular weight, leading to unexposed areas. As a result, the penetrability of the developer decreases and the developability deteriorates. Conversely, if the molecular weight is decreased for the purpose of improving developability, more components having a lower molecular weight than the desired molecular weight are mixed, and the photocurability of the dried coating film is improved, but the finger tack is deteriorated. End up.

  In addition, due to the demand for finer printed wiring boards, further improvement in the resolution of photographic development resist ink is desired, but it is formed by the current exposure and development processing of photographic development resist ink. The edge portion of the resist film is uneven and tends to be rough, and it is difficult to form a sharp shape that can cope with further refinement of photographic resist ink. This is due to the molecular weight distribution of the base resin in the photo-developing resist ink, resulting in non-uniformity in the solubility of the resist ink in the developing solution such as an organic solvent or an alkaline developer in the exposed and non-exposed portions. This is thought to be due to this.

  These problems occur because the molecular weight distribution in the base resin is wide, but it is difficult to narrow the molecular weight distribution. That is, an acrylic polymer often used as a base resin for a photo-developing resist is usually produced by radical polymerization, and the molecular weight distribution tends to be wide due to the nature of the polymerization method. In addition, it is difficult to control the monomer arrangement within the molecule, and when the monomers are charged all at once, the monomer composition between the polymers changes as the reaction proceeds. The polymer becomes a mixture of polymers having various monomer compositions. In addition, in order to solve this problem, there is a method in which the polymerization reaction proceeds while dropping the monomer in order to make the monomer composition in the polymer as uniform as possible between the polymers by the conventional radical polymerization method. Although it can be considered, it takes a long time to synthesize the polymer, and the uniformity of the molecular weight of the obtained polymer becomes insufficient.

  Therefore, it is considered to narrow the molecular weight distribution of the base resin by producing the base resin by a living radical polymerization method. The living radical polymerization method is a polymerization method characterized in that a growth radical is reversibly led to a stable dormant species. Compared with a normal radical polymerization method, the bimolecular termination reaction is less likely to occur, and the dispersity (Mw / A polymer having a narrow Mn) is obtained. Moreover, since the molecular weight of the polymer obtained is determined by the charge ratio of the initiating group and the monomer, the molecular weight can be easily set.

  Conventional living radical polymerization methods include those based on dissociation-bonding mechanisms using stable radicals such as nitroxide compounds, and those based on atom transfer radical polymerization methods that cause reversible radicalization by extracting halogens of organic halides with transition metal complexes. The radical addition and splitting of a chain transfer agent such as a dithioester compound (RAFT agent) reversibly causes an exchange reaction to be roughly classified into those by a reversible addition-cleavage chain transfer polymerization method.

  However, in the living radical polymerization method using a dissociation-bonding mechanism using a nitroxide compound or the like, there are problems that the monomer species to be subjected to polymerization are limited and the reaction temperature is high.

  Further, the atom transfer radical polymerization method has a problem that it is difficult to remove the catalyst (transition metal complex) remaining in the product.

  Further, when the reversible addition-cleavage chain transfer polymerization method is used, the above problem is solved (see Patent Document 3), but since the sulfur-based catalyst (chain transfer agent) is used, the product turns red. The problem remains that the product may be colored or the product may emit a strong odor.

  For this reason, not only a narrow molecular weight distribution but also a problem caused by the remaining of the catalyst during the living radical polymerization as described above is used in the resist ink composition, and a base resin that is available more simply and at low cost is used. It has come to be required.

  Accordingly, the present inventors have found a reversible transfer catalytic polymerization method (see Patent Document 4) as a new living radical polymerization method, and have searched for a catalyst that can be used in this reversible transfer catalytic polymerization method. As a result, the inventors have intensively studied the applicability of the resin synthesized by the above method to the base resin in the photosensitive resin composition.

JP 2003-252938 A JP 2004-264773 A JP 2007-025152 A Japanese Patent Laid-Open No. 2007-92014

The present invention has been made in view of the above points, and is excellent in low tackiness, photocurability, developability and resolution, and is free from problems caused by the remaining of the catalyst when the base resin is produced. Method for producing photosensitive resist ink composition for producing printed wiring board comprising conductive resin composition, method for producing cured product produced using this photosensitive resist ink composition for producing printed wiring board , and printed wiring board An object of the present invention is to provide a manufacturing method .

The photosensitive resin composition according to the present invention is characterized by containing the following component (A).
(A) A resin comprising at least one of a polymer obtained by a reversible transfer catalytic polymerization method and having a dispersity of 1.8 or less and a resin obtained by modifying this polymer.

  This composition can be suitably used as an etching resist ink, solder resist ink, etc. for the production of printed wiring boards. At this time, since it contains a resin having a narrow molecular weight distribution generated by a reversible transfer catalytic polymerization method, it has a high molecular weight. Prevents deterioration of developability due to mixing of components and reduced penetration of developer into non-exposed areas of dry coating, and deterioration of dry touch due to low molecular weight components. In addition, unevenness in the developability distribution in the non-exposed portion of the dried coating film is less likely to occur, and a dried coating film having uniform developability can be formed. In addition, it is not necessary to use a transition metal complex or a sulfur-based chain transfer agent as a catalyst during the synthesis of the component (A), and since the reactivity is good and the amount of the catalyst compound used can be reduced, Eliminates the need for removal and eliminates problems such as increased conductivity, coloration, and odor remaining due to the remaining catalyst, and allows the polymerization reaction to proceed efficiently under mild conditions. Be able to get.

The photosensitive resin composition according to the present invention preferably contains the following component (B) and component (C).
(B) Photopolymerizable monomer (C) Photopolymerization initiator In this case, the photosensitive resin composition exhibits photosensitivity by containing the component (B) and the component (C). The physical properties of the cured product can be adjusted by the component B).

Moreover, the photosensitive resin composition which concerns on this invention contains the following (C) component, and it is also preferable that the said (A) component has photosensitivity.
(C) Photopolymerization initiator In this case, the photosensitive resin composition can exhibit photosensitivity because the component (A) itself has photosensitivity.

  The component (A) is preferably an alkali-soluble resin. In this case, the non-exposed portion of the dry coating film of the photosensitive resin composition can be developed and removed using an alkaline solution as a developer.

  The component (A) preferably contains a resin having a carboxyl group in the side chain. In this case, alkali solubility can be imparted to the component (A), and the unexposed portion of the dry coating film of the photosensitive resin composition can be developed and removed using an alkaline solution as a developer. In addition, it is possible to introduce an alkali-soluble group into the component (A) by polymerization of a monomer having a carboxyl group or addition of an acid anhydride to a hydroxyl group in the polymer, and when other alkali-soluble groups are introduced. In comparison, there are advantages that the raw material having a carboxyl group is easily available and the introduction reaction is easy. In particular, when the component (G) described later is used as a resist ink component, there is an advantage that the coating film performance can be easily improved by the reaction between the carboxyl group and the epoxy group.

  Moreover, it is also preferable that the said (A) component contains resin which has an ethylenic double bond in a side chain. In this case, photosensitivity can be imparted to the component (A) by an ethylenic double bond, and the curability of the composition and the physical properties of the cured product can be adjusted.

  In addition, the component (A) is obtained by a reversible transfer catalytic polymerization method, and a polymer (A1) having a carboxyl group in a side chain is formed as a part of the carboxyl group and at least one ethylenic double molecule in the molecule. It is also preferable to include a resin obtained by modification by reacting with a compound (d) having a bond and a reactive group capable of reacting with at least one carboxyl group. Since such a component has a carboxyl group and an ethylenic double bond introduced into the component (A) by synthesis in only two steps, and can impart sufficient coating performance as a temporary coating to the composition, In particular, it can be suitably used as an etching resist ink.

  The component (A) is obtained by a reversible transfer catalytic polymerization method, and a polymer having an epoxy group in the side chain is substituted with a saturated or unsaturated monocarboxylic acid (e) in part or all of the epoxy group. It is also preferable to include a resin obtained by modifying a polybasic acid anhydride (f) with a part of the hydroxyl group produced by the reaction. More carboxyl groups and ethylenically unsaturated double bonds can be introduced into such components, which makes it easy to improve the performance of the coating film formed from the composition as a permanent coating film. Therefore, the composition can be suitably used particularly as a solder resist ink.

  In the reversible transfer catalytic polymerization method, a catalyst compound having at least one central element selected from germanium, tin, antimony, phosphorus, nitrogen, oxygen, and carbon and at least one halogen bonded to the central element is used. be able to.

  In the reversible transfer catalytic polymerization method, a compound having at least one hydroxyl group bonded to carbon, silicon, nitrogen, or phosphorus can be used as a catalyst precursor corresponding to a catalyst compound having oxygen as a central element. .

  In the reversible transfer catalytic polymerization method, a carbon compound can also be used as a catalyst precursor corresponding to a catalyst compound having carbon as a central element.

  In the reversible transfer catalytic polymerization method, iodine and an azo compound may be added to the reaction system before the start of polymerization, and an organic halide generated by the in-situ reaction may be used as a dormant species.

Moreover, it is also preferable to contain the following (G) component in the above compositions.
(G) Polyfunctional epoxy compound In this case, the composition can be given thermosetting properties, and further cured by photo-curing to further improve the cured product properties such as strength, hardness and chemical resistance. Is something that can be done.

Moreover, it is also preferable to contain the following (H) component in a composition.
(H) Diluent In this case, the resin component of the composition can be dissolved and diluted in the component (H) to make the composition ready for application as a liquid, and after application of the composition by drying ( The component H) can be volatilized to form a dry coating film.

  The photosensitive resist ink composition for producing a printed wiring board according to the present invention is characterized by comprising the photosensitive resin composition as described above.

  Moreover, the hardened | cured material which concerns on this invention is formed by hardening-molding the above-mentioned photosensitive resist ink composition for printed wiring board manufacture on a board | substrate. This cured product has excellent properties as a resist for manufacturing printed wiring boards.

  The printed wiring board according to the present invention is characterized by having a layer made of the cured product. In this case, a resist having good film characteristics can be formed on the printed wiring board with the layer made of the cured product.

  According to the present invention, there is no deterioration in developability and finger tack due to the wide molecular weight distribution of the base resin, and all the performances such as touch tack, photocurability and developability are all good. A composition can be obtained, and since it is excellent in resolution, a fine and sharp pattern can be formed, and in particular, it can cope with further refinement of recent printed wiring boards. Is something that can be done. Further, it is possible to eliminate problems such as an increase in conductivity and residual odor due to a catalyst used at the time of synthesis of the base resin, and it is possible to efficiently synthesize the base resin. It is possible to improve performance while improving performance.

  Hereinafter, the best mode for carrying out the present invention will be described.

[Components of photosensitive resin composition]
First, components for preparing a photosensitive resin composition (hereinafter referred to as a composition) will be described.

<< (A) Base resin >>
(Reversible transfer catalytic polymerization method)
In the present invention, the component (A) is synthesized through a reversible transfer catalyst polymerization method (RTCP; Reversible chain transfer catalyzed polymerization). The reversible transfer catalytic polymerization method is a kind of living radical polymerization method. The basic concept of living radical polymerization is a reversible activation reaction of dormant species (Polymer-X) to a growing radical (Polymer.), As shown in the following formula. It is difficult to cause a reaction, and a polymer having a narrow dispersity (Mw / Mn) is obtained. Further, in the reversible transfer catalytic polymerization method, the molecular weight of the polymer is determined by the charge ratio of the initially added dormant species and the monomer, so that the molecular weight can be easily set.

  The reversible transfer catalytic polymerization method uses a transition metal complex as in the case of the atom transfer radical polymerization method and a chain transfer agent (RAFT agent) such as a dithioester compound as in the case of the reversible addition-cleavage chain transfer polymerization method. Without using the catalyst compound (X-A). In this polymerization, the growing radical (Polymer.) Generated by the action of a radical polymerization initiator or the like pulls out the halogen (X) of the catalyst compound (X-A), and the radical active species (A.) of the catalyst compound is dormant. Generate in situ with seed (Polymer-X). The radical active species (A.) acts as an activator of dormant species, and a growth radical (Polymer.) And a catalyst compound (X-A) are generated. This process is a reversible chain transfer to the catalyst compound (X-A), and the dormant species is catalytically activated by this reversible chain transfer. As a result, the polymerization reaction proceeds very efficiently. The following formula shows an example in which the halogen (X) is iodine (I).

  The bonding of halogen in the catalyst compound is required to be appropriate for the exchange of halogen with the growing radical. As long as the halogen bond is an appropriate compound as described above, even a compound having a substituent other than halogen can be used as a catalyst compound for the reversible transfer catalytic polymerization method.

(Catalyst compound)
Examples of the catalyst compound include compounds containing at least one central element selected from germanium, tin, antimony, phosphorus, nitrogen, oxygen, and carbon and at least one halogen bonded to the central element. The central element means an atom which is mainly responsible for catalytic action by combining with halogen among atoms constituting the catalyst compound.

  When the central element of the catalyst compound is germanium, phosphorus, nitrogen, oxygen, or carbon, it is possible to suppress the remaining conductive material in the component (A) to be generated. Further, germanium, phosphorus, nitrogen, oxygen, and carbon are advantageous in that they are less toxic to the human body and less harmful to the environment. In addition, since this catalyst compound exerts a catalytic action even when the amount used is small, especially when the central element is germanium, phosphorus, nitrogen, oxygen, carbon, toxicity to the human body and environmental impact. There is an advantage that a catalyst compound having a small influence is used and the amount of the catalyst compound used can be further reduced.

  When the catalyst compound has two or more central elements, at least one halogen is bonded to each central element. The halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine, bromine or iodine, more preferably bromine or iodine, and particularly preferably iodine. Two or more halogens may be present in one molecule of the catalyst compound. For example, two, three, or four halogens may be present in one molecule, and a plurality of halogens may be present. The number of halogens in one molecule of the catalyst compound is preferably 2-4. The plurality of halogens present in one molecule of the catalyst compound may be the same type of atom or different types of atoms.

  The catalyst compound may have a group other than halogen as necessary. For example, an arbitrary organic group or inorganic group may be bonded to the central element in the catalyst compound.

  The organic group may have a chain structure or a cyclic structure, and may have both a chain structure and a cyclic structure. Examples of the organic group include substituted or unsubstituted aryl groups (including heteroaryl groups, the same applies hereinafter), alkenyl groups, alkynyl groups, alkoxy groups, ester groups (such as aliphatic carboxylic acid esters), alkyl carboxyl groups, and alkyl groups. Examples thereof include a carbonyl group (such as a methylcarbonyl group) and a haloalkyl group (such as a trifluoromethyl group).

  The number of aromatic hydrocarbon rings constituting the aryl group may be one, two or more, and preferably 1 to 3. When there are a plurality of aromatic hydrocarbon rings, these rings may or may not be condensed. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group.

  The number of the substituents in the aryl group having a substituent is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. Moreover, the position of the substituent in this aryl group is arbitrarily selected. In particular, when the aryl group is a phenyl group having a substituent, the position of the substituent may be any of the ortho, meta, and para positions with respect to the central element, but the para position is particularly preferable.

  The number of double bonds that the alkenyl group has is at least one and may be two or more. The upper limit of the number of double bonds is not particularly limited, but may be 10 or less, or 5 or less. In addition, a structure in which double bonds and single bonds are alternately repeated is preferable. The alkenyl group may have a chain or cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. The double bond may be present in either a cyclic structure or a chain structure. The carbon number of the alkenyl group may be any natural number, but is preferably 1-30, more preferably 1-20. The alkenyl group may be a lower alkenyl group. In this case, the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 to 3. Specific examples of the alkenyl group include a vinyl group.

  The number of triple bonds that the alkynyl group has may be one or two or more. The upper limit of the number of triple bonds is not particularly limited, but may be 10 or less, or 5 or less. A structure in which triple bonds and single bonds are alternately repeated is preferable. The alkynyl group may have a chain structure or a cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. The double bond may be present in either a cyclic structure or a chain structure. The carbon number of the alkynyl group may be any natural number, but is preferably 1 to 30, and more preferably 1 to 20. The alkynyl group may be a lower alkynyl group. In this case, the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 to 3.

  The alkoxy group may have a chain or cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. The number of carbon atoms of the alkoxy group may be any natural number, but is preferably 1-30, and more preferably 1-20. The alkoxy group may be a lower alkoxy group. In this case, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and an isopropoxy group.

  The alkyl carboxyl group may have any cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. Although carbon number of this alkyl carboxyl group may be arbitrary natural numbers, 1-30 are preferable and 1-20 are more preferable. The alkylcarboxyl group may be a lower alkylcarboxyl group. In this case, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

  The alkylcarbonyl group may have any cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. The number of carbon atoms of the alkylcarbonyl group may be any natural number, but is preferably 1-30, and more preferably 1-20. The alkylcarbonyl group may be a lower alkylcarbonyl group. In this case, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

  The haloalkyl group may have any cyclic structure. In the case of a chain, it may be either a straight chain or a branched chain. In the case of a ring, it may be composed only of a ring structure or a structure in which a ring structure and a chain structure are combined. In the haloalkyl group, all hydrogens may be substituted with halogens, or only some hydrogens may be substituted with halogens. Although the carbon number of this haloalkyl group may be arbitrary natural numbers, 1-30 are preferable and 1-20 are more preferable. The haloalkyl group may be a lower haloalkyl group. In this case, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Preferable specific examples of the lower haloalkyl group include a trifluoromethyl group.

  If this organic group is a substituted or unsubstituted aryl group, alkenyl group or alkynyl group, the radical activity during the reaction tends to be higher. Examples of the substituent when the aryl group has a substituent include an alkyl group and an alkyloxy group. The alkyl group is preferably a lower alkyl group. 1-5 are preferable and, as for carbon number of this lower alkyl group, if it is 1-3, it is especially preferable. More preferably, this lower alkyl group is a methyl group. That is, the organic group is preferably a phenyl group, a lower alkylphenyl group, or a lower alkyloxyphenyl group.

  Examples of the inorganic group include a hydroxyl group, an amino group, and a cyano group.

  The number of organic groups and inorganic groups in the catalyst compound is not particularly limited, but is preferably 3 or less, more preferably 1.

  The catalyst compound preferably does not have a radical reactive double bond.

  In addition, the catalyst compound may be a complex in which the ligand is coordinated by incorporating a ligand in the reaction system during the polymerization reaction, but such a ligand is not used. May be. For this reason, the transition metal complex used in the atom transfer radical polymerization method is improved in solubility by being complexed with a ligand, but the above catalyst compound uses such a ligand. There is no need. If a ligand is not used, it is advantageous in terms of material cost, and it is also advantageous in that the weight of the catalyst used can be reduced. That is, an amine compound generally used as a ligand is usually expensive or requires complicated labor for synthesis. Furthermore, considering the properties of the amine, it is considered that the amine complex of the transition metal is likely to be adsorbed on the produced polymer, and therefore it is considered that it takes more time to remove it.

  Many of such catalyst compounds are known, and those commercially available from reagent sales companies or the like can be used as they are. This catalyst compound can also be synthesized by a known method.

(Catalyst compounds with germanium, tin, and antimony as central elements)
An example of a catalyst compound having germanium as a central element is a catalyst compound having a structure in which an organic group such as an aryl group is bonded to germanium as R ¹ . This catalyst compound can be synthesized by a known method. For example, a catalyst compound having a structure of R ¹ GeI ₃ can be obtained by reacting iodide (R ¹ I) having a structure in which R ¹ is bonded to iodine as shown in the following reaction formula with germanium iodide (GeI ₂ ). Can be synthesized.

R ¹ I + GeI ₂ → R ₁ GeI ₃
When iodide (R ¹ I) is a liquid, the above reaction can proceed without using a solvent, but a solvent (for example, benzene, toluene, etc.) may be used if necessary. When iodide (R ¹ I) is a solid, for example, benzene, toluene, etc. can be used as a solvent. Note that this reaction proceeds even if no reaction catalyst is used. Specific examples of such reactions are described in, for example, the document Journal of Organometallic Chemistry 56, 1-39 (1973), and various R ¹ can be converted to germanium by applying the method described in this document. A compound bound to can be synthesized.

An example of a catalyst compound having tin as a central element is a catalyst compound having a structure in which an organic group such as an aryl group is bonded to tin as R ¹ . This catalyst compound can be synthesized by a known method. For example, by reacting SnI ₄ with a compound having a structure in which R ¹ is bonded to tin ((R ¹ ) ₄ Sn), (R ¹ ) _n SnI _m (n + m = 4 and n = 1, 2, or 3 ) Can be synthesized. Specific examples of such reactions are described in, for example, the literature Angewandte Chemie 75, 225-235 (1963), and various R ¹ bonds to tin by applying the method described in this literature. A compound having the above structure can be synthesized.

  A catalyst compound having antimony as a central element and an organic group such as an aryl group bonded thereto can be synthesized by a known method. For example, it can be synthesized by the same method as in the case where the central element is germanium or tin.

  The amount of the catalyst compound having germanium, tin or antimony as a central element is not particularly limited during the polymerization reaction and may be an amount sufficient to catalyze the living radical polymerization. It is preferably 10 mmol (mM) or less, preferably 5 mmol or less, and preferably 2 mmol or less. On a mass basis, the amount of catalyst compound used is preferably 1% by mass or less, more preferably 0.50% by mass or less, and also preferably 0.1% by mass or less based on the reaction solution.

  In addition, the lower limit of the amount of the catalyst compound used is not particularly limited, but is 0.1% per 1 liter of the reaction solution. It is preferably 1 mmol or more, preferably 0.5 mmol or more, and preferably 0.8 mmol or more. On a mass basis, the amount of catalyst compound used is preferably 0.01% by mass or more, preferably 0.05% by mass or more, and preferably 0.08% by mass or more based on the reaction solution. When the usage-amount of a catalyst compound is too small, the molecular weight distribution of the component (A) to produce | generate tends to become wide.

(Catalyst compounds with phosphorus and nitrogen as central elements)
Examples of the catalyst compound having phosphorus or nitrogen as a central element include those represented by the following general formula.

R ¹ _n M _h X ¹ _m Z _k
M is a central element and is phosphorus or nitrogen. X ¹ is halogen. Z is oxygen, nitrogen or sulfur. Z is bonded to M, and the bond between the two is a double bond or a triple bond. This bond is preferably a double bond when Z is oxygen or sulfur, and is preferably a triple bond when Z is nitrogen.

R ¹ in the formula is an organic group or an inorganic group, and is any ^one of an alkyl group, an alkyl carboxyl group, a haloalkyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group, an alkylcarbonyl group, a substituted or unsubstituted aryl group. And more preferably an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group. In particular, when the central element is phosphorus, R ¹ is preferably an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group.

n is an integer of 0 to 4 × h, and particularly preferably an integer of 0 to 2 × h. When R ¹ is plural (when n is 2 or more), each R ¹ may be the same as each other, or all R ¹ or a part of R ¹ may be different from each other. When R ¹ is plural (when n is 2 or more), two R ¹ may be bonded to each other and form a cyclic structure together with M.

  h is an integer of 1 or more, and is practically preferably an integer of 10 or less, more preferably an integer of 6 or less, further preferably an integer of 4 or less, and an integer of 3 or less. More preferably, an integer of 2 or less is particularly preferable, and 1 is most preferable. If h is too large, synthesis of the catalyst compound may be difficult.

  When h is an integer of 2 or more, the plurality of central elements M are preferably all the same element. When h is an integer of 2 or more, the central elements M are connected by a single bond, a double bond, or a triple bond. For example, when h is 2, a structure in which two central elements M are combined such as -M-M-, -M = M-, -M≡M- can be obtained. Specific examples include a structure of -P = P- in which two phosphorus atoms described later are bonded. When h is 3 or more, the central element M may be connected in a straight chain, for example, like -P = PP = P-, or may be connected in a branched chain.

Further, when h is an integer of 2 or more, R ¹ , X ¹ and Z may be independently bonded to any of the plurality of central elements M.

m is an integer of 1 to 5 × h, preferably an integer of 2 to 5 × h. When m is 2 or more, each X ¹ may be the same as each other, and all X ¹ or a part of X ¹ may be different from each other, but in particular, all X ¹ may be the same. preferable.

  k is an integer of 0 to 2 × h. When Z is nitrogen, k is preferably 0 or 1.

  When the central element M is phosphorus or nitrogen, m + n is preferably 3 or 5.

  Further, the values of n, h, m, and k are selected so that the overall valence of the catalyst compound is balanced.

R ¹ , X ¹ and Z in the formula are usually bonded to the central element M. For example, as a catalyst compound having a structure in which two central elements M are bonded (-M = M-), one having a structure of R ¹ -M = M-X ¹ can be mentioned.

  Preferred examples of the catalyst compound when the central element is phosphorus include those represented by the following general formula.

R ¹ _{n Ph} X ¹ _m (= O) _k
In this case, n is an integer of 0 to 2, preferably 0 when P is trivalent, and preferably 2 when P is pentavalent. k is 0 or 1, preferably 0 when P is trivalent, and preferably 1 when P is pentavalent. X ¹ is preferably iodine. R ¹ is preferably an alkoxy group or a substituted or unsubstituted aryl group, more preferably an alkoxy group or an unsubstituted aryl group, and particularly preferably a lower alkoxy group or an unsubstituted aryl group.

Specific examples of the catalyst compound in the case where the central element is phosphorus include phosphorus halides (phosphorous triiodide, phosphorus pentaiodide, etc.), halogenated phosphines (R ¹ ₂ PX ¹ , R ¹ PX ¹ ₂ etc.), for example Diphenylphosphine iodide (Ph ₂ PI)), halogenated phosphorous acid derivatives (R ¹ ₂ PX ¹ (═O), R ¹ PX ¹ ₂ (═O), PX ¹ ₃ (═O), etc.) Diethyl phosphite ((C ₂ H ₅ O) ₂ PI (═O)), ethylphenylphosphinate (Ph (C ₂ H ₅ O) ₂ PI (═O)), diphenylphosphine oxide (Ph ₂ PI (= O)).

On the other hand, when the central element is nitrogen, n is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. H is preferably 1, and k is preferably 0. Also, the two R ¹ in the case where two of R ¹ to form a nitrogen with cyclic structure is a central element, together alkylcarbonyl group is preferably a vinyl group, or a phenyl group.

Specific examples of the catalyst compounds if the central element is nitrogen, halogenated nitrogen (nitrogen triiodide), halogenated amine or halogenated imide _{^{(R 1 2 NX 1, R}} 1 NX 1 2 etc., for example iodine Diphenylamine (Ph ₂ NHI), succinimide iodide ((CH ₂ ) ₂ (C═O) ₂ NI (NIS)), maleimide iodide ((CH) ₂ (C═O) ₂ NI), iodide Examples thereof include phthalimide (C ₆ H ₄ (C═O) ₂ NI) and derivatives obtained by introducing one or more substituents into these compounds.

  The catalyst compound having phosphorus or nitrogen as a central element can be synthesized by a known method.

R, for example, as a method of synthesizing a catalyst compound having R ¹ to the phosphorus is a halogen and organic group bonded structure, iodoform to _{^{R 1 2 PH (= O)}} , iodine, or by reacting the N- iodosuccinimide A method of synthesizing ¹ ₂ PI (= O) is mentioned. Further, a catalyst compound in which halogen and an organic group R ¹ are bonded to phosphorus can also be synthesized by the methods described in the literature Chemical Communication 797-798 (2001) and the literature Synthetic Communication 33, 3851-3859 (2003).

In addition, as a method of synthesizing a catalyst compound having a structure in which halogen and an organic group R ¹ are bonded to nitrogen, R ¹ ₂ NI is synthesized by reacting R ¹ ₂ NH with iodine using Ag ₂ O as a catalyst. A method is mentioned. A catalyst compound in which halogen and an organic group R ¹ are bonded to nitrogen can also be synthesized by a method described in the document Journal of the American Chemical Society 75, 3494-3495 (1953).

  The amount of the catalyst compound having phosphorus or nitrogen as a central element during the polymerization reaction is not particularly limited and may be an amount sufficient to catalyze the living radical polymerization. It is preferably less than or equal to millimolar (mM), preferably less than or equal to 5 mmol, preferably less than or equal to 2 mmol, preferably less than or equal to 1 mmol, and preferably less than or equal to 0.5 mmol. On a mass basis, the amount of the catalyst compound used is preferably 1% by mass or less, preferably 0.75% by mass or less, and preferably 0.70% by mass or less, based on the reaction solution. .50% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and also preferably 0.05% by mass or less.

  Further, the lower limit of the amount of the catalyst compound used is not particularly limited, but is preferably 0.02 mmol or more, preferably 0.1 mmol or more, and 0.5 mmol or more with respect to 1 liter of the reaction solution. It is also preferable. On the mass basis, the amount of the catalyst compound used is preferably 0.001% by mass or more, preferably 0.005% by mass or more, and preferably 0.02% by mass or more with respect to the reaction solution. . When the usage-amount of a catalyst compound is too small, the molecular weight distribution of the component (A) to produce | generate tends to become wide.

  When a catalyst compound having phosphorus or nitrogen as a central element is used, the catalyst compound may be added directly to the polymerization reaction system, or a precursor of this catalyst compound (catalyst precursor) may be added. The catalyst precursor refers to a compound that does not correspond to a catalyst compound before being added to the polymerization reaction system, but can be chemically reacted in the polymerization reaction system to become a catalyst. “Becomes ready to act as a catalyst” preferably means that the catalyst precursor is converted to a catalyst compound.

  During the polymerization reaction, the catalyst compound becomes an activated radical and exhibits catalytic activity, but a compound that can generate an activated radical similar to the activated radical by a chemical reaction corresponds to the catalyst precursor. For example, phosphorus hydride corresponds to the catalyst precursor. That is, phosphorus hydride can generate an activated radical of a phosphorus compound by extracting hydrogen by a peroxide or the like. Nitrogen hydride also corresponds to the catalyst precursor.

Examples of the catalyst precursor corresponding to the catalyst compound having nitrogen as a central element include amines and imides (R ¹ ₂ NH or R ¹ NH ₂ , such as diphenylamine (Ph ₂ NH) and succinimide ((CH ₂ ) (C ═O) ₂ NH), maleimide ((CH) ₂ (CO) ₂ NH), phthalimide (C ₆ H ₄ (C═O) ₂ NH), and the like.

Examples of catalyst precursors corresponding to catalyst compounds having phosphorus as a central element include phosphites (R ¹ ₂ PH (═O)), specifically (EtO) ₂ PH (═O), (BtO). ₂ PH (= O), (EtO) PhPH (= O), etc. are mentioned. The phosphite may be a monoester of phosphonic acid or a diethyl ester. Among them, diethyl ester is preferable, and a dialkyl ester of phosphonic acid is more preferable.

  When such a catalyst precursor is used, the step of synthesizing component (A) includes a step of chemically changing the catalyst precursor before the polymerization reaction. It is advantageous in that the overall process can be simplified if the chemical change of the catalyst precursor is allowed to proceed in a vessel in which the polymerization reaction is performed, but it may be allowed to proceed in a vessel other than this vessel. .

  The amount of the catalyst precursor used can be the same as the amount of the catalyst compound used. The amount of activated radicals generated when this catalyst precursor is used is preferably the same amount as the amount of active radicals generated when the above amount of catalyst compound is used.

(Catalyst compound with oxygen as the central element)
In a catalyst compound having oxygen as a central element, the central element is bonded to an atom selected from carbon, silicon, nitrogen and phosphorus (hereinafter referred to as “position 1 atom” for convenience) in addition to halogen. The 1-position atom is preferably carbon, nitrogen or phosphorus, more preferably carbon. In addition to the central element, it is preferable that only other atoms selected from carbon and hydrogen (hereinafter, referred to as “2-position atom” for convenience) are bonded to the 1-position atom. The 2-position atom is preferably carbon. It is preferable that only an atom selected from carbon, oxygen and hydrogen is bonded to the 2-position atom. The bond between the 1-position atom and at least one 2-position atom is preferably a double bond or a triple bond. In this case, when an unpaired electron is generated in the central element and the catalyst compound is radicalized, a conjugated system is formed, resonance is stabilized, and the performance as a living radical polymerization catalyst is improved. Further, for example, it is preferable that two atoms exist as the 2-position atom, and one 2-position atom and the 1-position atom are bonded by a double bond. For example, it is preferable that two carbon atoms exist as the 2-position atom, and one of the carbon atoms and the 1-position atom are bonded by a double bond. Two or more 2-position atoms are preferably present. In this case, the 1-position atom and one 2-position atom are bonded by a double bond, and the other 2-position atom and 1-position atom are bonded by a single bond. It is preferable that the double bond and the single bond constitute a part of the conjugated system. For example, the first atom is carbon, there are two carbon atoms as the second atom, the bond between one 2-position atom and the first-position atom is a double bond, and the other 2-position atom and the first position It is preferable that the bond with the atom is a single bond, and the double bond and the single bond form part of a conjugated system. Specifically, for example, the central element is bonded to any organic group of an alkenyl group (such as a vinyl group), an alkynyl group, a substituted or unsubstituted aryl group (preferably a phenyl group, a biphenyl group, etc.), and When this organic group is an alkenyl group or an alkynyl group, it is preferable that a double bond or a triple bond exist at the terminal.

As preferred structure of the alkenyl group ^include those represented by -CR 7 = ^CR 8 ^{R 9.} R ⁷ , R ⁸ and R ⁹ may be hydrogen or an alkyl group, and other substituents (for example, alkenyl group, alkylcarboxyl group, haloalkyl group, alkylcarbonyl group, amino group, cyano group, alkoxy group, aryl group, An alkyl-substituted aryl group, etc.). When R ⁷ , R ⁸ , and R ⁹ are all hydrogen, the alkenyl group is a vinyl group.

Moreover, as a preferable structure of the alkenyl group, one represented by —C≡CR ¹⁰ can be mentioned. R ¹⁰ may be hydrogen or an alkyl group, and other substituents (for example, alkenyl group, alkyl carboxyl group, haloalkyl group, alkylcarbonyl group, amino group, cyano group, alkoxy group, aryl group, alkyl-substituted aryl group, etc.) It may be.

  Examples of the catalyst compound having oxygen as a central element include those represented by the following general formula.

R ¹ _n (OX ¹ ) _m
X ¹ is halogen.

R ¹ in the formula is an organic group or an inorganic group, and is an alkyl group, alkenyl group, alkynyl group, alkyl carboxyl group, haloalkyl group, hydroxyl group, amino group, cyano group, alkoxy group, alkylcarbonyl group, substituted or unsubstituted. Of the aryl group is preferable, and as described above, it is particularly preferable that the aryl group is any one of an alkenyl group, an alkynyl group, and a substituted or unsubstituted aryl group.

  n is a positive integer, for example, may be 1, may be 2, or may be an integer of 3 or more. Moreover, the integer of 1-10 may be sufficient as n, the integer of 1-5 may be sufficient, the integer of 1-3 may be sufficient, and 1 or 2 may be sufficient.

m is a positive integer, for example, may be 1, may be 2, or may be an integer of 3 or more. Moreover, the integer of 1-10 may be sufficient as m, the integer of 1-5 may be sufficient, the integer of 1-3 may be sufficient, and 1 or 2 may be sufficient. When m is 2 or more, each X ¹ may be the same as each other, and all X ¹ or a part of X ¹ may be different from each other, but in particular, all X ¹ may be the same. preferable.

  The values of n and m are selected so that the overall valence of the catalyst compound is balanced.

The central element oxygen is usually bonded to both R ¹ and X ¹ .

Specific examples of the catalyst compound having oxygen as a central element include halogenated oxygen (for example, oxygen iodide), alkoxy halide or carboxy halide (R ¹ OX, for example, benzoic acid iodide (PhCOOI)), phenol in a phenolic compound And compounds in which hydrogen in the hydroxyl group is substituted with halogen (for example, thymol iodide).

  A catalyst compound having oxygen as a central element can be synthesized by a known method. Moreover, the compound which exists in natural products, such as vitamins, can also be obtained by methods, such as extracting from a natural product.

For example, a method of synthesizing a catalyst compound having a structure in which halogen and an organic group R ¹ are bonded to oxygen includes a method of synthesizing R ¹ OI by reacting R ¹ OH with ICl. Further, as a method for synthesizing such a catalyst compound, described in literature Tetrahedron Letters 21, 2005-2008 (1980), literature Tetrahedron Letters 25, 1953-1956 (1984), literature Tetrahedron Letters 30,4791-4794 (1989), etc. The method which was made is also mentioned.

  The amount of the catalyst compound having oxygen as a central element during the polymerization reaction is not particularly limited as long as it is sufficient to catalyze the living radical polymerization. mM) or less, preferably 5 mmol or less, preferably 2 mmol or less, preferably 1 mmol or less, and preferably 0.5 mmol or less. On a mass basis, the amount of the catalyst compound used is preferably 1% by mass or less, preferably 0.75% by mass or less, and preferably 0.70% by mass or less, based on the reaction solution. .50% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and also preferably 0.05% by mass or less.

  Further, the lower limit of the amount of the catalyst compound used is not particularly limited, but is preferably 0.02 mmol or more, preferably 0.1 mmol or more, and 0.5 mmol or more with respect to 1 liter of the reaction solution. It is also preferable. On the mass basis, the amount of the catalyst compound used is preferably 0.001% by mass or more, preferably 0.005% by mass or more, and preferably 0.02% by mass or more with respect to the reaction solution. . When the usage-amount of a catalyst compound is too small, the molecular weight distribution of the component (A) to produce | generate tends to become wide.

  When a catalyst compound having oxygen as a central element is used, the catalyst compound may be added directly to the polymerization reaction system, or a precursor of this catalyst compound (catalyst precursor) may be added.

  Examples of the catalyst precursor corresponding to the catalyst compound having oxygen as the central element include compounds in which halogen bonded to oxygen, which is the central element in the catalyst compound having oxygen as the central element, is substituted with hydrogen. That is, a compound having a structure in which a hydroxyl group is bonded to an atom selected from carbon, silicon, nitrogen, and phosphorus can be used as the catalyst precursor.

  Examples of the catalyst precursor include a phenol compound having a structure in which a hydroxyl group is bonded to an aromatic ring, and an aliphatic alcohol compound having a structure in which a hydroxyl group is bonded to carbon of an aliphatic group.

It is preferable that the catalyst precursor does not have a radical reactive double bond. Double bonds having low reactivity with radicals such as aromatic double bonds (for example, double bonds in a benzene ring) may be present in the catalyst precursor. Even if it is an aliphatic double bond, the double bond with low reactivity with a radical like the double bond in vitamin C may exist in the catalyst precursor. Thus, vitamin C can be used as a catalyst precursor. In general, a double bond bonded to a hydroxyl group (a double bond between a 1-position atom and a 2-position atom) has no reactivity with a radical. Such as vinyl alcohol _(CH 2 = CH-OH) is not a radical polymerizable monomer. A triple bond bonded to a hydroxyl group (a triple bond between the 1-position atom and the 2-position atom) similarly has no radical reactivity, and a compound having such a triple bond is not a radical polymerizable monomer.

  It is also preferable to use a catalyst precursor that also has a function as an antioxidant. In general, it is considered that an antioxidant preferably has a large substituent in the vicinity of a hydroxyl group. However, such a large substituent is not used for a catalyst precursor having a function as an antioxidant. It doesn't have to exist. For example, even when there is no substituent other than a hydroxyl group, such as unsubstituted phenol, it can be used as a catalyst precursor that also functions as an antioxidant.

  The amount of the catalyst precursor used can be the same as the amount of the catalyst compound used. The amount of activated radicals generated when this catalyst precursor is used is preferably the same amount as the amount of active radicals generated when the above amount of catalyst compound is used.

  When a phenolic compound is used as a catalyst precursor, the phenolic compound may act as a polymerization inhibitor depending on the type of monomer if the amount used is large. For example, when polymerizing styrene or the like, the polymerization reaction may not proceed if the amount of the phenolic compound used is excessive. For this reason, it is desirable that the amount of the phenolic compound used is small enough not to act as a polymerization inhibitor. However, when the monomer is an acrylate or methacrylate, the phenolic compound does not become an effective polymerization inhibitor, so there is no disadvantage due to the polymerization inhibiting effect even if the amount of the phenolic compound used is large to some extent.

  Examples of catalyst compounds having oxygen as a central element and catalyst precursors corresponding to the catalyst compounds are shown in the following formula.

(Catalyst compound with carbon as the central element)
The catalyst compound having carbon as a central element includes carbon, which is a central element, and two or three electron-withdrawing substituents or substituents that form a resonance structure with the central element in addition to halogen. Can be mentioned. By having such a substituent, an active radical (carbon radical) is stabilized by the substituent when halogen is eliminated from the catalyst compound. Further, an electron donating substituent capable of stabilizing the carbon radical may be bonded to the central element. A compound in which 1 to 3, preferably 2 to 3, such electron donating substituents are bonded to the central element can be used as the catalyst compound. Hereinafter, the electron-withdrawing substituent, the substituent that forms a resonance structure with the central element, and the electron-donating substituent are collectively referred to as a radical stabilizing substituent.

  In addition, a substituent other than the radical stabilizing substituent may be bonded to the central element of the catalyst compound. The number of substituents other than the radical stabilizing substituent bonded to one central element is preferably 1 or less, and no substituent other than the radical stabilizing substituent is bonded to the central element. Is more preferable. Examples of the substituent other than the radical stabilizing substituent include hydrogen.

  In this catalyst compound, when two or three radical stabilizing substituents are bonded, the two radical stabilizing substituents are connected to each other, thereby The central element may form a ring structure. Further, when three radical stabilizing substituents are bonded to the central element, the three radical stabilizing substituents are connected to each other, so that the three radical stabilizing substituents and the central element are A ring structure may be formed. When a plurality of radical stabilizing substituents bonded to the same central element are connected to each other, the plurality of radical stabilizing substituents constitute one radical stabilizing substituent as a whole, It can be considered that a plurality of different atoms in the substituent for radical stabilization are bonded to the same central element. However, in this specification, for convenience, in such a case, it is considered that a plurality of substituents for radical stabilization are bonded to the central element.

  The electron-withdrawing substituent is a substituent that binds to carbon as a central element and attracts electrons from the central element. Preferred electron withdrawing substituents are halogens, specifically fluorine, chlorine, bromine or iodine. The electron-withdrawing substituent may be a substituent that attracts electrons from the central element to the same extent as halogen, such as carbonyl oxygen (═O), cyano group, and nitro group.

  The electron donating substituent is a substituent that bonds to the central element carbon and donates electrons to the central element. Examples of such electron donating substituents include alkoxy groups.

  Examples of the substituent that forms a resonance structure with the central element include a substituent having a double bond or a triple bond. In the substituent constituting the double bond or triple bond, an atom bonded to the central element (first-position atom) and an atom bonded to the first-position atom in the substituent (second-position atom) are double bonds or They are linked by a triple bond. In this case, when the central element is a carbon radical, the carbon radical is stabilized by the resonance effect of the carbon radical and the electron in the double bond or triple bond, and exhibits high activity as a catalyst. .

  Examples of the 1-position atom in the substituent having a double bond include carbon, silicon, phosphorus, nitrogen and the like. Examples of the 1-position atom in a substituent having a triple bond include carbon, silicon, phosphorus and the like. Is mentioned. In particular, the 1-position atom is preferably carbon. The 1-position atom may be bonded to other appropriate groups such as hydrogen and alkyl groups in addition to the central element and the 2-position atom. Examples of the 2-position atom in the substituent having a double bond include carbon, silicon, phosphorus, nitrogen, and oxygen. Examples of the 2-position atom in the substituent having a triple bond include carbon, Silicon, phosphorus, nitrogen, etc. are mentioned. In particular, the 2-position atom is preferably carbon. The 2-position atom may be bonded to other appropriate groups such as hydrogen and alkyl groups in addition to the central element and the 2-position atom.

  Moreover, it is particularly preferable that both the 1-position atom and the 2-position atom in the substituent having a double bond or a triple bond are carbon. When both the 1-position atom and the 2-position atom are carbon and both are bonded by a double bond, even if the double bond is an aromatic double bond, it is an ethylenic double bond. There may be. Examples of the substituent having such a double bond include an alkenyl group, an alkynyl group, a substituted or unsubstituted aryl group, and the like. However, since the catalyst compound is preferably not polymerized during the radical reaction, the substituent having a double bond is particularly preferably a substituted or unsubstituted aryl group. Moreover, it is preferable that the substituent having an ethylenic double bond has low radical polymerization reactivity.

  Moreover, it is preferable that two or three substituents having a double bond or a triple bond as described above are bonded to the central element. In this case, when the central element is a carbon radical, the carbon radical is further stabilized by the resonance effect, and exhibits higher activity as a catalyst.

  Examples of the catalyst compound include those represented by the following general formula.

X ¹ in the formula is halogen. In the formula, R ^a and R ^b are an organic group in which a 1-position atom and a 2-position atom are bonded by a double bond or a triple bond, or halogen, and R ^c is a 1-position atom and a 2-position atom. Is an organic group, halogen or hydrogen bonded with a double bond or triple bond. Any two selected from R ^a , R ^b , and R ^c may be connected to each other to form a ring structure including any two of R ^a , R ^b , and R ^c and the central element, A ring structure containing R ^a , R ^b and R ^c may be formed by connecting R ^a , R ^b and R ^c to each other. The central element, R ^a and R ^b may constitute an aliphatic unsaturated ring structure or an aromatic ring structure.

Examples of the catalyst compound include those represented by the general formula R ¹ X ¹ _h . R ¹ is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group. Examples of the substituent in the aryl group having a substituent include a lower alkyl group, a lower alkoxy group, and a cyano group. X ¹ is halogen and is bonded to a carbon atom in the aromatic ring of R ¹ . h is any positive integer not exceeding the number of carbon atoms in the aromatic ring of R ¹ .

  When two substituents constituting a resonance structure together with the central element are bonded to one central element, the two substituents and the central element preferably constitute one resonance structure as a whole. That is, for example, the two substituents and the central element preferably constitute an aromatic ring structure as a whole. An example of a catalyst compound having such a structure is iodobenzene. In this case, among the carbon atoms constituting the aromatic ring of iodobenzene, the 1st carbon bonded to iodine corresponds to the central element, and the 2nd and 5th carbon atoms are respectively the 1st atom of the substituent. Applicable. Moreover, the compound shown by the following general formula can also be mentioned as a catalyst compound which has such a structure.

Wherein, M ¹¹ is an atom binding to the carbon (C) is the central atom, preferably carbon, silicon, phosphorus or nitrogen, more preferably carbon. M ¹² is an atom bonded to M ¹¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, more preferably carbon or oxygen. The bond between M ¹¹ and M ¹² is a double bond or a triple bond. R ¹⁰ and R ¹¹ are any substituents present depending on the valence of M ¹¹ , R ¹² and R ¹³ are any substituents present depending on the valence of M ¹² , for example hydrogen An alkyl group, an alkoxy group, and the like.

M ²¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, more preferably carbon. M ²² is an atom bonded to M ²¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, more preferably carbon or oxygen. The bond between M ²¹ and M ²² is a double bond or a triple bond. R ²⁰ and R ²¹ are any substituents present depending on the valence of M ²¹ , R ²² and R ²³ are any substituents present depending on the valence of M ²² , for example hydrogen An alkyl group, an alkoxy group, and the like. R ¹³ may be linked to R ²³ .

  Other examples of the catalyst compound include compounds represented by the following general formula.

In the formula, M ⁴¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, more preferably carbon. M ⁴² is an atom binding to M ^41, preferably carbon, silicon, phosphorus, nitrogen or oxygen, more preferably a carbon or oxygen. R ⁴⁰ and R ⁴¹ are any substituents present depending on the valence of M ⁴¹ , and R ⁴² and R ⁴³ are any substituents present depending on the valence of M ⁴² , for example, hydrogen, alkyl Group, alkoxy group and the like.

M ⁵¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, more preferably carbon. M ⁵² is an atom bonded to M ⁵¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, more preferably carbon or oxygen. R ⁵⁰ and R ⁵¹ are any substituents present depending on the valence of M ⁵¹ , and R ⁵² and R ⁵³ are any substituents present depending on the valence of M ⁵² , for example hydrogen, alkyl Group, alkoxy group and the like.

In the general ^{formula, R 43} is ^{R 43} if may be coupled to the ^{R 53,} also further absent ^{R 53} may be connected to ^{M 52.} An example of the structure of the catalyst compound in such a case is shown in the following general formula.

In the catalyst compound represented by the above general formula, it is preferable that among atoms constituting R ⁴³ , an atom bonded to M ⁴² is also bonded to M ⁵² because a stable 6-membered ring can be formed. As an example of a preferable form of such a catalyst compound, R ⁴³ is CH or N, the bond between M ⁴² and R ⁴³ is a single bond, R ⁵³ is not present, and R ⁴³ is directly M ^52. And the bond between R ⁴³ and M ⁵² is a double bond. In this case, an extremely stable resonance structure is formed in the 6-membered ring.

Further, when both R ⁴³ and R ⁵³ are not present, M ⁴² may be directly bonded to M ⁵² . In this case, the carbon atom of the central element and M ⁴¹ , M ⁴² , M ⁵¹ and M ⁵² form a 5-membered ring.

  Note that the substituent constituting the resonance structure together with the central element may be an electron-withdrawing substituent or an electron-donating substituent.

Preferable specific examples of the catalyst compound having carbon as a central element include carbon halide (for example, CI ₄ ), alkyl halide or aryl halide (for example, diphenylmethane iodide (Ph ₂ Cl ₂ )), halogenated heteroaryl, and the like. Can be mentioned.

  The catalyst compound having carbon as a central element includes a compound corresponding to an organic halide, but this catalyst compound is distinguished from organic halides such as PE-I and CP-I used as dormant species. For example, when a catalyst compound corresponding to an organic halide is used, an organic compound having a structure different from that of the catalyst compound is used as the dormant species. A compound in which two or more methyl groups are bonded to carbon to which halogen is bonded, such as PE-I and CP-I, does not act as a catalyst. Since the organic halogen compound which is a catalyst compound has a strong affinity for halogen, it has a strong ability to pull out the halogen from the dormant species, and does not react with the monomer and must not be a growth seed for polymerization. This catalyst compound is preferably an organic halide that is slightly unstable electronically and highly active as compared with the dormant species, and is somewhat bulky in order to avoid reaction with the monomer. That is, the organic halide which is a catalyst compound has a weak carbon-halogen bond and is likely to release a halogen to become a carbon radical, and the carbon radical preferably has a strong ability to extract halogen from a dormant species.

The organic halide acts as a catalyst compound does not function as a dormant species, the radical is a catalyst based on electronic p orbital of the organic halide, or s-orbital and hybridized orbital of the p orbitals (e.g. sp ³ hybrid orbital) It works effectively. Such an organic halide functioning as a catalyst compound can be easily confirmed by conducting a radical reaction experiment. Specifically, an organic halide and a surrogate dormant species (for example, PE-I) were combined to conduct a living radical polymerization reaction. If a narrow molecular weight distribution was obtained, the organic halide acted as a catalyst. I can confirm that.

  Preferred specific examples of the catalyst compound having carbon as a central element are shown below.

  As a catalyst compound having a structure in which a halogen (preferably iodine) is directly bonded to an aromatic ring, those exemplified below can be used.

  As the catalyst compound having a structure in which halogen (preferably iodine) is bonded to carbon adjacent to the conjugated aliphatic double bond, those exemplified below can be used. This catalyst compound preferably has a structure in which iodine is bonded to carbon sandwiched between two double bonds.

  As the catalyst compound having a structure in which halogen (preferably iodine) is bonded to carbon adjacent to the aromatic double bond, those exemplified below can be used. This catalyst compound preferably has a structure in which halogen (preferably iodine) is bonded to carbon sandwiched between two or more aromatic rings. A compound having a structure in which a halogen (preferably iodine) is bonded to carbon sandwiched between three aromatic rings can also be used as a catalyst compound.

  As the catalyst compound having a structure in which a halogen (preferably iodine) is bonded to carbon adjacent to a double bond such as an ester bond, those exemplified below can be used. This catalyst compound preferably has a structure in which a halogen (preferably iodine) is bonded to carbon sandwiched between two double bonds.

In addition, a catalyst compound having a C—I (carbon-iodine) bond or a C—Br (carbon-bromine) bond and a structure in which carbon is further bonded to three halogen atoms can be used. For example a catalyst compound represented by the general formula CX ¹ _m I _n can be used. X ¹ is halogen, m and n are each an integer of 1 to 3, and m + n = 4. That is, methyl tetrahalide having at least one iodine or bromine can be used as a catalyst compound. Examples of such a catalyst compound include CI ₄ , CF ₃ I, CF ₂ I _{2 and the} like. Note that methyl halide (for example, CCl ₄ ) having neither I nor Br is not preferable because its activity as a catalyst is very low.

  A catalyst compound having carbon as a central element can be synthesized by a known method. Moreover, the compound which exists in a natural product can also be obtained by methods, such as extracting from the natural product.

For example, as a method of synthesizing a catalyst compound having a structure in which halogen and an organic group R ¹ are bonded to carbon, R ¹ ₃ CH is reacted with N-iodosuccinimide, R ¹ ₃ COH is iodine or P ₂ I Or a method of synthesizing R ¹ ₃ I by reacting ₄ or the like. Moreover, as a method of synthesizing such a catalyst compound, methods described in the document Tetrahedron Letters 36, 609-612 (1995) and the document Tetrahedron Letters 20, 1801-1904 (1979) can also be mentioned.

  The amount used of the catalyst compound having carbon as a central element during the polymerization reaction is not particularly limited as long as it is sufficient to catalyze the living radical polymerization. mM) or less, preferably 5 mmol or less, preferably 2 mmol or less, preferably 1 mmol or less, and preferably 0.5 mmol or less. On a mass basis, the amount of the catalyst compound used is preferably 1% by mass or less, preferably 0.75% by mass or less, and preferably 0.70% by mass or less, based on the reaction solution. It is also preferably 0.5 mass% or less, preferably 0.2 mass% or less, preferably 0.1 mass% or less, and preferably 0.05 mass% or less.

  Further, the lower limit of the amount of the catalyst compound used is not particularly limited, but is preferably 0.02 mmol or more, preferably 0.1 mmol or more, and 0.5 mmol or more with respect to 1 liter of the reaction solution. It is also preferable. On the mass basis, the amount of the catalyst compound used is preferably 0.001% by mass or more, preferably 0.005% by mass or more, and preferably 0.02% by mass or more with respect to the reaction solution. . When the usage-amount of a catalyst compound is too small, the molecular weight distribution of the component (A) to produce | generate tends to become wide.

  When a catalyst compound having carbon as a central element is used, the catalyst compound may be added directly to the polymerization reaction system, or a precursor (catalyst precursor) of this catalyst compound may be added.

  Examples of the catalyst precursor corresponding to the catalyst compound having carbon as the central element include compounds in which halogen bonded to carbon, which is the central element in the catalyst compound having carbon as the central element, is substituted with hydrogen.

  Therefore, for example, a compound having a structure in which one or two hydrogen atoms and two or three radical stabilizing substituents are bonded to carbon as a central element can be used as a catalyst precursor. . As the substituent for radical stabilization, a substituent constituting a resonance structure together with the central element is preferable. Carbon, which is the central element, may be bonded to one substituent other than the hydrogen atom and the radical stabilizing substituent, but it is more preferable that such a substituent is not bonded to the central element. .

  However, a compound having a structure in which a halogen is directly bonded to an aromatic ring can be used as a catalyst compound, but a compound in which the halogen of this compound is substituted with hydrogen (aromatic cyclic hydrocarbon such as benzene) is active as a catalyst. Is not preferable as a catalyst precursor.

  Further, methyl halide can be used as a catalyst compound, but a compound (methane) in which all halogens of this methyl halide are substituted with hydrogen is difficult to use as a catalyst precursor because it is a gas, and its activity is also low. Therefore, it is not preferable.

  Examples of the compound having a structure in which a halogen bonded to a carbon atom in the catalyst compound is substituted with hydrogen include a compound having a structure in which a C—H group is bonded to carbon, silicon, nitrogen, or phosphorus.

  The catalyst precursor is preferably a compound having a structure in which two aromatic rings are bonded to methylene.

  In the catalyst precursor, the atom (position 1 atom) bonded to carbon as a central element other than halogen includes carbon, silicon, nitrogen or phosphorus, preferably carbon, nitrogen or phosphorus, more preferably carbon. is there. It is preferable that only an atom selected from carbon and hydrogen is bonded to the 1-position atom, in addition to carbon as a central element. The atom other than the central element bonded to the 1st atom (2nd atom) is preferably carbon. It is preferable that only an atom selected from carbon, oxygen and hydrogen is bonded to the 2-position atom. Further, the bond between the 1-position atom and the 2-position atom is preferably a double bond. Further, it is preferable that two 2-position atoms are bonded to the 1-position atom, and one 2-position atom and the 1-position atom are bonded by a double bond, for example, to the carbon atom that is the 1-position atom. It is preferable to use a catalyst precursor having a structure in which two carbon atoms are bonded as the 2-position atom, and the carbon atom which is the 1-position atom and the carbon atom which is one 2-position atom are bonded by a double bond. . Two or more 2-position atoms are preferably present. In this case, the 1-position atom and one 2-position atom are bonded by a double bond, and the other 2-position atom and 1-position atom are bonded by a single bond. It is preferable that the double bond and the single bond constitute a part of the conjugated system. For example, the first atom is carbon, there are two carbon atoms as the second atom, the bond between one 2-position atom and the first-position atom is a double bond, and the other 2-position atom and the first position It is preferable that the bond with the atom is a single bond, and the double bond and the single bond form part of a conjugated system.

  As such a catalyst precursor, a hydrocarbon compound having a structure in which a hydrocarbon group is bonded to an aromatic ring is preferable. For example, a compound in which a hydrocarbon group is bonded to a substituted or unsubstituted aryl group is preferable. For example, it is preferable to use a compound having a structure in which two aromatic substituents are bonded to a methylene group as the catalyst precursor. The aryl group is preferably a substituted or unsubstituted phenyl group or biphenyl group. In addition, the substituent in the aryl group having a substituent is preferably an alkyl group, an alkoxyl group, a cyano group or the like, and more preferably a lower alkyl group or a lower alkoxy group.

  The catalyst precursor preferably does not have a radical reactive double bond. The catalyst precursor may have a double bond having low reactivity with a radical such as an aromatic double bond (for example, a double bond of a benzene ring). Even if it is an aliphatic double bond, the compound which has a double bond with low reactivity with a radical has no trouble in using as a catalyst precursor.

  Preferred specific examples of the catalyst precursor corresponding to the catalyst compound having carbon as a central element are shown below.

  A compound having a structure in which hydrogen is bonded to carbon adjacent to an aliphatic double bond can be used as a catalyst precursor. In particular, a compound in which hydrogen is bonded to carbon sandwiched between two aliphatic double bonds can be used. For example, a compound having a methylene group sandwiched between two aliphatic double bonds can be used. Examples of such a catalyst precursor include 1,4-cyclohexadiene represented by the following formula.

  A compound in which hydrogen is bonded to carbon adjacent to an aromatic ring can be used as a catalyst precursor. In particular, a compound in which hydrogen is bonded to carbon sandwiched between two or more aromatic rings can be used. For example, examples of the catalyst precursor having a methylene group sandwiched between two aromatic rings include those represented by the following formula. Triphenylmethane is an example of a catalyst precursor having a structure in which hydrogen is bonded to carbon sandwiched between three aromatic rings.

  A compound having a structure in which hydrogen is bonded to carbon adjacent to a double bond such as an ester bond can be used as a catalyst precursor. In particular, a compound having a structure in which hydrogen is bonded to carbon sandwiched between two double bonds can be used as a catalyst precursor. For example, a compound having a methylene group sandwiched between two double bonds can be used as a catalyst precursor. Examples of such a catalyst precursor include those represented by the following formula.

  (A) The combination of the kind of monomer used for the synthesis | combination of a component, and a catalyst compound is not specifically limited, It is possible to use the catalyst compound arbitrarily selected with respect to the monomer selected arbitrarily. However, for methacrylate monomers, it is preferable to use a catalyst compound having a substituent having an aromatic ring, more specifically, a catalyst compound having an aryl group, from the viewpoint of reactivity. .

(Dormant species)
In living radical polymerization using this catalyst compound, it is preferable to introduce a protective group for protecting this growing chain into the growing chain in the course of the reaction in the polymerization reaction system. Examples of such protecting groups include various known protecting groups conventionally used for protecting living radical polymerization.

  In introducing the protective group, as a dormant species, for example, an organic halide having a carbon-halogen bond is added to the polymerization reaction system, and the halogen is transferred from the organic halide to the growing chain, whereby the halogen is used as a protective group. can do. Since such organic halides are relatively inexpensive, they are advantageous over other known compounds for introducing protective groups in living radical polymerization. In addition, a dormant species in which a halogen is bonded to an element other than carbon can be used as necessary.

  The organic halide is not particularly limited as long as it has at least one carbon-halogen bond in the molecule and functions as a dormant species. It is preferable that one or two halogen atoms are contained in one molecule.

  The number of hydrogen atoms bonded to the halogen-bonded carbon of the organic halide (hereinafter referred to as “1-position carbon” for convenience) is preferably 2 or less, more preferably 1 or less, and hydrogen is bonded. It is particularly preferred that Further, when the halogen bonded to the 1-position carbon of the organic halide is chlorine, the number of chlorine is preferably 3 or less, more preferably 2 or less, and preferably 1. Particularly preferred.

  One or more carbon atoms are preferably bonded to the 1-position carbon of the organic halide, and more preferably 2 or 3 carbon atoms are bonded.

  The halogen of the organic halide may be the same as or different from the halogen in the catalyst compound. This is because even if the halogens are different, the halogens can be exchanged between the organic halide and the catalyst compound. However, it is preferable that the halogen of the organic halide and the halogen in the catalyst compound are the same because the exchange of the halogen between the organic halide and the catalyst compound is easier.

  Examples of the organic halide include those represented by the following general formula (II).

CR ² R ³ R ⁴ X ² (II)
Here, R ² and R ³ in the formula are each independently halogen, hydrogen or an alkyl group, preferably hydrogen or a lower alkyl group, more preferably hydrogen or a methyl group. R ⁴ is halogen, hydrogen, an alkyl group, an aryl group or a cyano group, preferably an aryl group or a cyano group. When R ⁴ is a halogen, hydrogen or an alkyl group, R ⁴ may be the same as or different from R ² or R ³ .

X ² is halogen, preferably chlorine, bromine or iodine. When halogen exists in R ^{2 to} R ⁴ , X ² may be the same as or different from the halogen in R ^{2 to} R ⁴ . X ² may be the same as or different from the halogen contained in the catalyst compound.

  The number of halogens contained in one molecule of the organic halide is preferably 1 or 2.

  Preferable examples of such organic halides include alkyl halides and halogenated substituted alkyls. Of these, halogenated substituted alkyl is particularly preferred. The alkyl group in this halogenated alkyl or halogenated substituted alkyl is preferably a secondary or higher alkyl group, more preferably a tertiary alkyl group. In other words, the carbon to which the halogen of the organic halide is bonded preferably has 2 or less, more preferably 1 or less, and even more preferably no hydrogen.

  In the halogenated alkyl or halogenated substituted alkyl, the alkyl group preferably has 2 or 3 carbon atoms. Therefore, the organic halide is more preferably halogenated substituted ethyl or halogenated substituted isopropyl. In addition, examples of the substituent in the halogenated substituted alkyl include a phenyl group and a cyano group.

Preferable specific examples of the organic halide include, for example, PE-I (CH (CH ₃ ) (Ph) I), CP-I (C (CH ₃ ) ₂ (CN) I) represented by the following structural formula: Etc.

  Other specific examples of the organic halide include, for example, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, bromomethyl, dibromomethane, bromoform, tetrabromomethane, bromoethane, dibromoethane, Tribromoethane, tetrabromoethane, bromotrichloromethane, dichlorodibromomethane, chlorotribromomethane, iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, tetraiodomethane, iodoform , Diiodomethane, methyl iodide, isopropyl chloride, t-butyl chloride, isopropyl bromide, t-butyl bromide, triiodoethane, ethyl iodide, diiodopro Emissions, isopropyl iodide, iodide t- butyl, bromo dichloroethane, chloro-dibromoethane, bromo chloroethane, iodo dichloroethane, chloro diiodo ethane, di-iodopropane, chloro iodopropane, iodo-dibromoethane, and bromo-iodopropane and the like. These organic halides may be used alone or in combination of two or more.

  The amount of the organic halide used in the polymerization reaction is preferably 0.05 or more, more preferably 0.5 mol or more, and more preferably 1 mol or more per 1 mol of the radical polymerization initiator in the polymerization reaction system. More preferred. The amount used is preferably 100 moles or less per mole of radical polymerization initiator in the polymerization reaction system, more preferably 30 moles or less, and even more preferably 5 moles or less. Further, the amount used is preferably 0.001 mol or more, and more preferably 0.005 mol or more per mol of the vinyl monomer supplied to the polymerization reaction system. The amount used is preferably 0.5 mol or less per mol of the vinyl monomer supplied to the polymerization reaction system, more preferably 0.4 mol or less, and 0.3 mol or less. If it is more preferable if it is 0.2 mol or less, it is more preferable if it is 0.1 mol or less. Further, the amount used is preferably 0.07 mol or less per mol of the vinyl monomer, preferably 0.05 mol or less, and preferably 0.04 mol or less, It is also preferably 0.03 or less, preferably 0.02 mol or less, and preferably 0.01 mol or less.

  Many compounds of the organic halide are known. As the organic halide, a reagent commercially available from a reagent sales company or the like can be used as it is. The organic halide can also be synthesized using a conventionally known synthesis method.

  Alternatively, an organic halide raw material can be charged into the polymerization reaction system, and the organic halide can be generated in situ during the polymerization reaction. For example, by introducing azobis (isobutyronitrile) and iodine as raw materials into the polymerization reaction system, the above-mentioned CP-I which is an organic halide can be generated in situ during the polymerization reaction.

  Moreover, what was fixed to the inorganic or organic solid surface, the inorganic or organic molecular surface, etc. can also be used for an organic halide. For example, an organic halide immobilized on the surface of a silicon substrate, the surface of a polymer film, the surface of an inorganic or organic fine particle, the surface of a pigment, or the like can be used. For immobilization, for example, chemical bonds or physical bonds can be used.

(Radical reaction initiator)
In the living radical polymerization method using this catalyst compound, a necessary amount of radical reaction initiator can be used as needed. As a radical reaction initiator, a well-known initiator can be used as an initiator used for radical reaction. For example, as the radical reaction initiator, an azo radical reaction initiator, a peroxide radical polymerization initiator, or the like can be used. Specific examples of the azo-based radical reaction initiator include azobis (isobutyronitrile). Specific examples of the peroxide radical polymerization initiator include benzoyl peroxide and dicumyl peroxide.

  Moreover, when using a hydrogenated compound as a catalyst precursor, it is preferable to use a peroxide type radical polymerization initiator as a radical reaction initiator. Since the peroxide-based radical polymerization initiator has a particularly strong ability to extract hydrogen from a hydrogenated compound, it can generate activated radicals by extracting hydrogen from a catalyst precursor such as a hydride of phosphorus. As the peroxide, an organic peroxide is particularly preferable.

  Although the usage-amount of a radical polymerization initiator is not specifically limited, 1 mmol or more is preferable with respect to 1 liter of reaction liquid, 5 mmol or more is more preferable, and 10 mmol or more is still more preferable. The amount of the radical polymerization initiator used is preferably 500 mmol or less, more preferably 100 mmol or less, and even more preferably 50 mmol or less with respect to 1 liter of the reaction solution.

  Further, when the polymerization reaction takes a long time, it is preferable to add these radical reaction initiators to the reaction system continuously little by little, or add little by little.

(Solvent, etc.)
A solvent can be used during the polymerization reaction. If the reaction mixture containing the monomer and the like used for the synthesis of the component (A) is liquid at the reaction temperature, it is not always necessary to use a solvent, but in this case as well, a solvent may be used as necessary. As the solvent, it is possible to use a solvent conventionally used for living radical polymerization as it is, for example, water, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol, Linear, branched, secondary or polyhydric alcohols such as ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Swazil series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso Petroleum-based aromatic mixed solvents such as series (manufactured by Exxon Chemical); cellosolves such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; propyleneglycol such as propyleneglycol methyl ether Kill ethers; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Acetic esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; Dialkyl glycol ethers Etc. can be used. Such organic solvents can be used alone or in combination of two or more.

  The amount of the solvent used is not particularly limited as long as the polymerization reaction is properly performed, but it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the monomer. If it is more preferable. If the amount of solvent used is too small, the viscosity of the reaction solution may become too high. Moreover, it is preferable that the usage-amount of this solvent is 2000 mass parts or less with respect to 100 mass parts of monomers, More preferably, it is 1000 mass parts or less, More preferably, it is 500 mass parts or less. If the amount of the solvent used is too large, the monomer concentration of the reaction solution may become too thin.

  When a solvent that does not dissolve the monomer is used, emulsion polymerization, dispersion polymerization, and suspension polymerization can be performed. For example, when styrene or methacrylate is used as a monomer, emulsion polymerization, dispersion polymerization, and suspension polymerization can be performed by using water as a solvent.

  Further, necessary amounts of various additives may be added to the polymerization reaction system as necessary. Examples of the additive include an antioxidant and a polymerization inhibitor.

(Reaction conditions)
By mixing the various raw materials described above, a raw material composition suitable as a material for living radical polymerization can be obtained, and living radical polymerization can proceed in this raw material composition.

  This raw material composition preferably contains no raw materials other than the above raw materials. For example, from the viewpoint of environmental problems, the raw material composition preferably does not substantially contain a raw material containing a transition metal. Moreover, it is preferable that a raw material composition does not contain material (for example, episulfide compound etc.) unrelated to living radical polymerization substantially.

  For example, the raw material composition contains at least one of a radical polymerization initiator, a catalyst compound and a catalyst precursor, a monomer used for the synthesis of the component (A), a solvent, and an organic halide, and substantially contains other raw materials. It is preferable not to include. In addition, when using a catalyst precursor, it is preferable that the radical polymerization initiator is a peroxide radical polymerization initiator as described above. Moreover, when a solvent is unnecessary, the solvent does not need to be contained.

  The reaction temperature during the polymerization reaction is not particularly limited, but when a catalyst compound having germanium, tin, or antimony as a central element is used, the reaction temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. More preferably, it is 40 degreeC or more, and it is especially preferable if it is 50 degreeC or more. The reaction temperature is preferably 130 ° C. or lower, more preferably 110 ° C. or lower, further preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 85 ° C. or lower.

  When using a catalyst compound having phosphorus, nitrogen, oxygen or carbon as a central element, the reaction temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, further preferably 30 ° C. or higher, further preferably 40 ° C. If it is more, it is more preferable, and if it is 50 degreeC or more, it is especially preferable. The reaction temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, further preferably 110 ° C. or lower, even more preferably 105 ° C. or lower, and particularly preferably 100 ° C. or lower.

  When this reaction temperature is too high, there is a drawback that the cost for heating equipment is increased. When the temperature is lower than room temperature, there is a disadvantage that costs are required for equipment for cooling. In addition, when a reaction mixture is prepared so as to polymerize at room temperature or lower, the reaction mixture is unstable and reacts at room temperature, which makes it difficult to store the reaction mixture. Therefore, the above temperature range that is slightly higher than room temperature and not excessively high (for example, when using a catalyst compound having germanium, tin, or antimony as a central element, 50 to 85 ° C., phosphorus or nitrogen as a central element) In the case of using the compound to be used is very suitable in a practical sense.

  The reaction time for the polymerization reaction is not particularly limited, but is preferably 15 minutes or longer, more preferably 30 minutes or longer, and even more preferably 1 hour or longer. The reaction time is preferably 3 days or less, more preferably 2 days or less, and even more preferably 1 day or less.

  When this reaction time is too short, it is difficult to obtain the component (A) having a sufficient molecular weight. If the reaction time is too long, the overall efficiency of the process is poor. By setting an appropriate reaction time, excellent performance (moderate polymerization reaction rate and reduction of side reactions) can be achieved.

  This polymerization reaction may be performed in an air atmosphere. Moreover, you may carry out in inert gas atmosphere, such as nitrogen and argon, as needed.

  The resulting polymer obtained by this living radical polymerization has a halogen such as iodine at the terminal. This terminal halogen can be removed or converted to other functional groups as required. Since the terminal halogen is generally highly reactive, it can be removed or converted to other functional groups by various reactions. For example, a method of removing terminal iodine with heat or energy rays, a method of converting terminal iodine into sodium hydroxide by reacting with sodium hydroxide, a method of converting terminal iodine into sodium chloride by reacting with sodium chloride, terminal iodine Can be reacted with sodium borohydride to convert it to hydrogen, terminal iodine can be reacted with alcohol to convert it to an alkoxy group, and terminal iodine can be reacted with amine to convert it to an amino group. . Halogens other than iodine can be converted into various functional groups as in the case of iodine.

(Configuration of component (A))
The component (A) is obtained by a reversible transfer catalyst polymerization method, a polymer having a dispersity of 1.8 or less, and a polymer obtained by a reversible transfer catalyst polymerization method and having a dispersity of 1.8 or less. It consists of at least one among resin obtained. Dispersity (Mw / Mn) is defined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). The degree of dispersion can be derived based on the measurement result of molecular weight by GPC (gel permeation chromatography).

  The monomer used for the synthesis of the component (A) may be any copolymerizable ethylenically unsaturated monomer. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl Linear, branched or alicyclic alkyl (meth) acrylates such as (meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Hydroxyalkyl (meth) acrylates such as meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; polyethylene Mono (meth) acrylates of polyalkylene glycols such as glycol and polypropylene glycol (the number of alkylene glycol units is 2 to 23, for example); methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, tri Ethylene glycol ester (meth) acrylates such as ethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and the like Propylene glycol-based (meth) acrylates, butylene glycol-based mono (meth) acrylates; amino group containing such as dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate (meta ) Acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide, N-tertiary butyl (meta) ) Acrylamides such as acrylamide, N-tertiary octyl (meth) acrylamide, diacetone (meth) acrylamide; styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene, o-hy Vinyl aromatics such as loxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl alcohol Compounds; maleimides such as maleimide, N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 2- (meth) acrylamide ethanesulfonic acid, 2- (meth) acrylamidepropanesulfonic acid, 3- (meth) acrylamide (Meth) acrylates containing sulfonic acid groups such as propanesulfonic acid; glycerol mono (meth) acrylate, vinyl acetate, vinyl ethers, (meth) allyl alcohol, vinylidene cyanide, vinyl chloride, vinylidene chloride, vinyl Pyrrolidone, and (meth) acrylonitrile.

  Further, a compound having a plurality of copolymerizable ethylenically unsaturated groups can be used in a small amount for the synthesis of the component (A) as long as gelation does not occur. Such polyfunctional compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, etc. . These can be used alone or in combination of two or more. These compounds are used to adjust the hardness of the pre-cured coating film and the final resist hardness when resist ink is used, or work on the resist ink use process such as dispersibility, solubility, and printability. Used for sex control and so on.

  As a method of introducing an alkali-soluble group into the component (A) to obtain an alkali-soluble type, a monomer having one radical polymerizable double bond and one or more alkali-soluble groups in the molecule is reversible. An appropriate reactive group is previously introduced into the polymer obtained by the transfer catalyst polymerization method and the polymer obtained by the reversible transfer catalyst polymerization method, and the functional group reacting with the reactive group is added to the polymer. And a method of reacting a compound having an alkali-soluble group or a compound that reacts and bonds with the reactive group to generate a carboxyl group. Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group.

  As the component (A), those having photosensitivity can be used, but those having no photosensitivity can also be used. Photosensitivity means the property of causing a polymerization reaction upon irradiation with energy rays such as ultraviolet rays, visible rays, infrared rays, and electron beams in the presence of an appropriate photopolymerization initiator.

  Specific examples of such component (A) include the following components (A1) to (A3).

  (A1) A polymer having a carboxyl group in the side chain.

  (A2) Obtained by reacting a part of the carboxyl group of the component (A1) with a compound (d) having a reactive group capable of reacting with at least one ethylenic double bond and one carboxyl group in the molecule. resin.

  (A3) After producing a polymer having an epoxy group in the side chain, all or part of the epoxy group is reacted with a saturated or unsaturated monocarboxylic acid (e), and all or all of the hydroxyl groups in the product are reacted. Resin obtained by partially reacting polybasic acid anhydride (f).

  The component (A1) contains at least one copolymerized monomer (monomer) having at least one copolymerizable ethylenically unsaturated group as at least one or all of the monomers to be polymerized. This polymerization can be carried out by a reversible transfer catalytic polymerization method as described above using a compound having an ionic double bond and at least one carboxyl group.

  Examples of the compound having one ethylenic double bond and at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid and the like; succinic anhydride, maleic anhydride, phthalic anhydride, and the like. Dibasic acid anhydrides such as acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride And hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate Reaction with compounds having an ethylenically unsaturated group containing one hydroxyl group in one molecule such as rate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate Half esters obtained by succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic acids such as itaconic acid and glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Examples include half esters obtained by reacting a compound having an ethylenically unsaturated group containing one epoxy group in one molecule such as tomonoglycidyl ether.

  Such compounds can be used alone or in combination of two or more. Among these, (meth) acrylic acid can be mentioned as a particularly preferred compound.

  When the component (A2) is produced from the component (A1), the component (d) (compound having a reactive group capable of reacting with at least one ethylenic double bond and one carboxyl group in the molecule) is used. Can include compounds having a glycidyl group, an isocyanate group or the like as a reactive group capable of reacting with a carboxyl group. Specifically, as a compound having a glycidyl group, glycidyl (meth) acrylate, (3,4-epoxydicyclohexyl) methyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Licar Resin ESA”) and the like are 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK; product number “ Karenz AOI ”, 2-methacryloyloxyethyl isocyanate (Showa Denko KK; product number“ Karenz MOI ”) and the like.

  The component (A2) has photosensitivity because it has an ethylenic double bond derived from the component (d) in the side chain.

  This (d) component can be used individually or in combination of multiple types. As the component (d), glycidyl (meth) acrylate is particularly preferably used.

  When the component (d) is reacted with the component (A1), it is preferable to set the addition amount of the component (d) so that the acid value of the component (A2) is in the range of 20 to 200 mgKOH / g.

  Moreover, it is preferable to use a catalyst in order to promote this reaction at the time of reaction of (A1) component and (d) component. Examples of the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. The amount of the catalyst used is the total amount of the reaction raw material mixture (finally the total amount of raw materials contained in the reaction system), that is, the monomers used for the production of the component (A1), the solvent, the catalyst used in the living radical polymerization method, and The total amount of the initiator, the component (d), the catalyst used for the reaction of the component (d), the polymerization inhibitor used for the reaction of the component (d) is preferably in the range of 0.1 to 10% by mass. .

  In the reaction of the component (A1) with the component (d), a polymerization inhibitor is preferably used for the purpose of preventing the polymerization reaction of the component (A1). Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The amount of the polymerization inhibitor used is preferably 0.01 to 1% by mass with respect to the total amount of the reaction raw material mixture.

  The component (A1) and the component (d) can be reacted at a reaction temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method. The reaction time is preferably 5 to 60 hours.

  When obtaining the component (A3), first, a compound (monomer) having at least one copolymerizable ethylenically unsaturated group is polymerized to synthesize a polymer having an epoxy group in the side chain. A compound having one ethylenic double bond and at least one epoxy group in the molecule is used as at least part or all of the monomer to be subjected to this polymerization. This polymerization is performed by the reversible transfer catalytic polymerization method as described above.

  Examples of the compound having one ethylenic double bond and at least one epoxy group in the molecule include glycidyl (meth) acrylate, (3,4-epoxydicyclohexyl) methyl (meth) acrylate, β-methylglycidyl ( Examples thereof include (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Rikaresin ESA”) and the like. These compounds can be used alone or in combination of two or more. As this compound, glycidyl (meth) acrylate is particularly preferably used.

  Among the components (e) (saturated or unsaturated monocarboxylic acid), examples of the saturated monocarboxylic acid include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, isovaleric acid, and pivalin. Acid, palmitic acid, stearic acid, benzoic acid, glycolic acid, lactic acid, glyceric acid, dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid, and the like can be used.

  When an unsaturated monocarboxylic acid is used as the component (e), an ethylenic double bond can be introduced into the side chain of the component (A3), thereby imparting photosensitivity to the component (A3). can do. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid, etc .; succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydroanhydride Dibasic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipe Half esters obtained by reacting a compound having an ethylenically unsaturated group containing one hydroxyl group in one molecule such as taerythritol penta (meth) acrylate and tripentaerythritol hepta (meth) acrylate; succinic acid, Dibasic acids such as maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, itaconic acid and glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate monoglycidyl ether, etc., containing one epoxy group in one molecule Examples include half esters obtained by reacting a compound having an ethylenically unsaturated group.

  This (e) component can be used individually by 1 type or in combination of multiple types. Moreover, as this (e) component, it is especially preferable to use (meth) acrylic acid.

  The component (f) (polybasic acid anhydride) reacts with a hydroxyl group generated by the reaction between a polymer having an epoxy group in the side chain and the component (e). Thereby, a carboxyl group is introduced into the side chain of the component (A3), and alkali solubility is imparted to the component (A3). Examples of the component (f) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride. And dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride and itaconic anhydride, and trimellitic anhydride. A compound having one or more acid anhydride groups can also be used in a small amount within the range where gelation does not occur. For example, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, diphenylsulfonetetra Carboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 5- (2,5-dioxo And tetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (“B-4400” manufactured by Dainippon Ink & Chemicals, Inc.).

  In the production of the component (A3), when the component (e) is reacted with the polymer having an epoxy group in the side chain, the component (e) is added in an amount of 0.7 to 1 epoxy equivalent of the polymer. It is preferable to use in the range of 1.2 chemical equivalents.

  Moreover, it is preferable to use a catalyst in order to promote the reaction between the polymer having an epoxy group in the side chain and the component (e). Examples of the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. The amount of this catalyst used is the total amount of the reaction raw material mixture (finally the total amount of raw materials contained in the reaction system), that is, the monomers used for the production of the component (A3), the solvent, the catalyst used in the living radical polymerization method, and Preferably 0.1 to 10 mass with respect to the total amount of initiator, (e) component, (f) component, catalyst used for reaction of (e) component, polymerization inhibitor used for reaction of (e) component, etc. % Range.

  Moreover, at the time of reaction with the polymer which has an epoxy group in a side chain, and (e) component, it is preferable to use a polymerization inhibitor in order to prevent superposition | polymerization of the polymers which have an epoxy group in a side chain. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The amount used is preferably 0.01 to 1% by mass with respect to the total amount of the reaction raw material mixture.

  The reaction conditions for the polymer having an epoxy group in the side chain and the component (e) are appropriately set, but the reaction is preferably carried out by a conventional method at a reaction temperature of 60 to 150 ° C., particularly preferably 80 to 120 ° C. . The reaction time is preferably 5 to 60 hours.

  In reacting the component (f) with the intermediate product produced by the reaction of the polymer having an epoxy group in the side chain with the component (e), depending on the desired acid value to be imparted to the component (A3), It is preferable to use the component (f) in the range of 0.1 to 1.5 chemical equivalents relative to one hydroxyl group equivalent of the intermediate product.

  Further, during the reaction of this intermediate product with the component (f), the same catalyst as in the case of the reaction with the component (e) is used to promote the reaction, and the polymerization of the intermediate product is prevented. For the purpose, it is preferable to use the same polymerization inhibitor as in the case of the reaction with the component (e). As this catalyst and polymerization inhibitor, those added in the reaction with the component (e) can be used as they are.

  This intermediate product and component (f) can be reacted at a reaction temperature of preferably 20 to 150 ° C., particularly preferably 50 to 100 ° C., by a conventional method. The reaction time is preferably 1 to 30 hours.

  The above components (A1) and (A2) and component (A3) can both be used for preparing the composition as an etching resist ink or a solder resist ink. In particular, the components (A1) and (A2) can be synthesized by a one-step or two-step reaction, and have alkali solubility and photosensitivity by having a carboxyl group and an ethylenic double bond. By using the component (A1) and the component (A2), a composition having sufficient coating film performance as an etching resist ink can be prepared. For this reason, (A1) component and (A2) component can be used suitably in order to prepare a composition as an etching resist ink. In addition, the component (A3) requires a three-stage reaction to synthesize, but more carboxyl groups and ethylenically unsaturated double bonds can be introduced into the component (A3). When the component) is used, it is easy to improve the performance of a permanent coating film having a high required level of coating film performance. For this reason, the component (A3) can be suitably used particularly when the composition is prepared as a solder resist ink.

  The component (A) as described above is a polymer having a dispersity (Mw / Mn) of 1.8 or less obtained by the reversible transfer catalyst polymerization method, or a dispersity (Mw / Mn) obtained by the reversible transfer catalyst polymerization method. Is composed of a resin obtained by modifying a polymer having a molecular weight of 1.8 or less, the degree of dispersion of the component (A) is also narrow. Here, when the degree of dispersion of the polymer obtained by the reversible transfer catalyst polymerization method becomes wider than 1.8, a component having a higher molecular weight than a desired molecular weight and a component having a lower molecular weight enter the system. Although the developability of the exposed area is lowered and the photocurability of the dried coating film is improved by the low molecular weight component, the finger tack is deteriorated. That is, it becomes difficult to achieve both finger touch, photo-curing property, and developability. In order to obtain a composition having more excellent performance, the degree of dispersion of the polymer is preferably 1.6 or less, and more preferably 1.5 or less. Further, it is desirable that the degree of dispersion of the component (A) is 1.8 or less.

  Here, although the theoretical lower limit of the degree of dispersion of the polymer obtained by the reversible transfer catalytic polymerization method is 1, it is difficult to set the degree of dispersion to 1, and the actual lower limit of the degree of dispersion is 1.05.

  Here, the dispersity can be adjusted by changing the living radical polymerization conditions by the reversible transfer catalytic polymerization method in the synthesis of the component (A), and the living radical polymerization conditions can be changed as appropriate. By doing so, the degree of dispersion of the component (A) can be made as desired. In other words, the parameters that determine the molecular weight distribution of the living radical polymerization system include the activation rate constant and growth radical concentration in the reversible activation of the dormant species, and the living radical polymerization system with a large activation rate constant of the dormant species should be selected. Thus, the molecular weight distribution of the obtained polymer can be narrowed and the degree of dispersion can be narrowed.

  In addition, since the occurrence frequency of the bimolecular termination reaction can be suppressed by lowering the growth radical concentration, the molecular weight distribution can be narrowed and the degree of dispersion can be narrowed. For example, the amount of radical initiator that is a radical source is reduced.

  The number average molecular weight of the component (A) is preferably in the range of 1000 to 200000, more preferably 2000 to 100000. Within such a range, developability and finger tackiness are ensured.

  Furthermore, in order to impart sufficient alkali solubility to the component (A), the acid value is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 170 mgKOH / g.

  This component (A) is contained in an appropriate ratio in the composition, but the total amount of the composition (when the diluent (H) is contained in the composition, the diluent (H) is excluded). The total amount of the composition) is preferably 10 to 90% by mass. In this case, the composition has good photosensitivity and workability, and good physical properties of the finally formed cured film. Can be secured.

<< (B) Photopolymerizable monomer >>
As the component (B), a photopolymerizable monomer such as a (meth) acrylate monomer can be used. Examples of such a photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholine, methoxytetraethylene glycol (meta ) Acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N , N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (Meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobonyl (meth) acrylate , Cyclopentanyl mono (meth) acrylate, cyclopentenyl mono (meth) acrylate, cyclopentanyl di (meth) a Lilate, cyclopentenyl di (meth) acrylate; mono-, di-, tri- or higher polyesters of polybasic acid and hydroxyalkyl (meth) acrylate; polyester (meth) acrylate, urethane (meth) acrylate, etc. Can be mentioned.

  This component (B) is blended in the composition to dilute the composition and make it easy to apply, and adjust the acid value of the composition to adjust the alkali solubility of the entire composition. It may also have a function.

  Moreover, this (B) component becomes a component for providing photosensitivity to a composition, when using what does not have photosensitivity as said (A) component, and said (A) component is Even if it has photosensitivity, if the component (B) is further contained in the composition, further photosensitivity can be imparted to the composition.

  When blending the component (B) in the composition, it is 50 masses relative to the total amount of the composition (total amount excluding the organic solvent when an organic solvent is used as the component (H) (diluent) described later). It is preferable to make it contain in the range of% or less. When the component (B) exceeds 50% by mass in the composition, the surface adhesiveness of the dry coating film of the composition becomes too strong, and the negative mask on which the pattern is drawn is directly applied to the dry coating film surface. May cause problems such as contamination of the negative mask. Further, the lower limit of the content when the component (B) is contained in the composition is not particularly limited, but the lower limit is set to 1% by mass in order to impart photosensitivity for obtaining good film properties to the composition. It is preferable to do.

<< (C) Photopolymerization initiator >>
(C) It does not restrict | limit especially as a component, The photoinitiator for desired energy ray exposures, such as an ultraviolet-ray, visible light, infrared rays, near infrared rays, an electron beam, can be used. Specific examples of the component (C) include, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 -Acetophenones such as diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4 Thioxanthones such as diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, 1-chloro-4-propoxythioxanthone; acetophenone dimethylketa And ketals such as benzyl dimethyl ketal; benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxylcarbonyl) benzophenone, 4-benzoyl-4 ′ -Benzophenones or xanthones such as methyldiphenyl sulfide; 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,4,4′-bis-diethylaminobenzophenone and the like containing nitrogen atoms; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

  These components (C) can be contained alone or in combination in the composition.

  In addition to these (C) components, benzoic acid-based or tertiary amine-based light such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, etc. A polymerization accelerator or a sensitizer may be used in combination. Further, as a sensitizer for laser exposure method, coumarin derivatives such as 7-diethylamino-4-methylcoumarin, 4,6-diethyl-7-ethylaminocoumarin, other carbocyanine dyes, xanthene dyes, etc. are appropriately selected. May be used.

  In the case where this component (C) is blended in the composition, the blending amount is appropriately set. In order to obtain a good balance between the photosensitivity of the composition and the physical properties of the resulting cured film, The total amount of the composition is preferably in the range of 0.1 to 30% by mass based on the total amount of the composition (the total amount excluding the organic solvent when an organic solvent is used as the component (H) (diluent) described later).

<< (G) Polyfunctional epoxy compound >>
When the component (G) is blended in the composition, it can impart thermosetting properties to the composition and can impart a wide development width. The development width means a range of predrying conditions that can maintain developability, and is also referred to as a predrying management width or a predrying allowable range.

  As this (G) component, a solvent hardly soluble epoxy compound, a general purpose solvent soluble epoxy compound, etc. can be used, for example. Specifically, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolac type epoxy resin, bisphenol F type epoxy resin, triglycidyl isocyanurate, biphenyl type epoxy resin (for example, Product number “YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, product number “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.), polyol Polyglycidyl ether compound, glycidyl ester compound, N-glycidyl type epoxy resin, tris (hydroxydiphenyl) methane based polyfunctional epoxy resin (for example, product number “EPPN-50 manufactured by Nippon Kayaku Co., Ltd.) H ”, product numbers“ TACTIX-742 ”and“ XD-9053 ”manufactured by Dow Chemical Co., Ltd.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene-phenol type epoxy resin, naphthalene type epoxy resin, vinyl polymerization having an epoxy group Examples thereof include polymers and polyisocyanate-modified products of polyfunctional glycidyl compounds. These can be used individually by 1 type or in combination of multiple types.

  Of these, triglycidyl isocyanurate, biphenyl type epoxy resin (for example, product number “YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type, among others as component (G) It is desirable to use an epoxy resin, a bisphenol A-novolak type epoxy resin, or the like.

  (G) When mix | blending a component in a composition, the compounding quantity is the whole quantity of an ultraviolet curable resin composition (When using an organic solvent as (H) component (diluent) mentioned later, this organic solvent is used. Is preferably in the range of 0.1 to 50% by mass, and particularly in the range of 0.1 to 30% by mass, the composition is imparted with excellent thermosetting and wide development width. The

<< (H) Diluent >>
An organic solvent can be used as this (H) component. Examples of the organic solvent include linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol; methyl ethyl ketone and cyclohexanone. Ketones such as toluene; Aromatic hydrocarbons such as toluene and xylene; Petroleum aromatic mixed solvents such as Swazil series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolves such as carbitol, carbitol such as butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol such as dipropylene glycol methyl ether Le alkyl ethers; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve sol blanking acetate, butyl carbitol acetate, acetic acid esters such as propylene glycol monomethyl ether acetate; dialkyl glycol ethers, and the like. Further, water can be used as the component (H), or water and a hydrophilic organic solvent can be used in combination. In this case, in order to disperse and emulsify or solubilize the organic component, a surfactant or the like can be used in combination. When water is used, it is less burdensome on the environment in that unnecessary release of the organic solvent can be reduced.

  This (H) component can be used alone or in combination of two or more as appropriate.

  When this (H) component is used, the resin component of the composition can be dissolved and diluted so that the composition can be applied as a liquid, and after application of the composition, the (H) component is volatilized by drying. Thus, a dry coating film can be formed. In particular, when the composition is prepared as a resist ink that can be developed with a dilute alkaline solution, it is preferable to include an organic solvent as the component (H) in the composition. At this time, an appropriately selected organic solvent is used. Thus, it is preferable that the component (H) volatilizes quickly during preliminary drying and does not remain in the dried coating film.

  When the component (H) is contained in the composition, the blending amount is desirably 5% by mass or more based on the total amount of the composition. When the amount is less than this, it is difficult to apply the composition. In addition, since the suitable compounding quantity of this (H) component changes with the application | coating methods of a composition, it is preferable to adjust a compounding quantity suitably according to the coating method selected.

<< (I) Other ingredients >>
In the composition, particularly when preparing the composition as a photo solder resist ink, in addition to the above components, for example, tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate blocked with caprolactam, oxime, malonic acid ester, etc. Thermosetting components such as hexamethylene diisocyanate-based blocked isocyanates and amino resins such as n-butylated melamine resins, isobutylated melamine resins, butylated urea resins, butylated melamine urea cocondensed resins, benzoguatemine based cocondensed resins, And UV curable epoxy acrylate or UV curable epoxy methacrylate, such as bisphenol A type, phenol novolac type, cresol novolac type, alicyclic type epoxy resin, acrylic acid or methacrylic , And styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid resin, diallyl phthalate resin, phenoxy resin, melamine resin, urethane resin, fluorine resin, etc. Can be blended.

  In addition, this composition may further contain an epoxy resin curing agent such as imidazole derivatives, polyamines, guanamines, tertiary amines, quaternary ammonium salts, polyphenols, polybasic acid anhydrides, melamine, dicyandiamide and the like as necessary. And curing accelerators; fillers and colorants such as barium sulfate, silicon oxide, talc, clay, calcium carbonate; leveling agents such as silicon, acrylate copolymers and fluorosurfactants; adhesion of silane coupling agents, etc. Property imparting agent; thixotropic agent such as aerosil; polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine; various additives such as antihalation agent, flame retardant, antifoaming agent, antioxidant; Surfactant and polymer dispersion to improve dispersion stability Or the like may be blended.

  Moreover, as long as the objective of this invention can be achieved, a composition may contain the other resin synthesize | combined through polymerization methods other than a living radical polymerization method other than the said (A) component. Examples of such other resins include resins synthesized in the same manner as the component (A) except that they are synthesized through a polymerization method other than the living radical polymerization method instead of the reversible transfer catalytic polymerization method. it can. In addition, in the case where the component (A) does not have photosensitivity, a resin having photosensitivity as another resin can be contained in the composition in order to impart photosensitivity to the composition. The content of the other resin is appropriately adjusted so that the dispersity of the base resin does not become excessively wide.

[Method for Preparing Photosensitive Resin Composition]
The composition of the present invention can be prepared by mixing each of the above components by an appropriate technique. For example, each compounding component and additive can be prepared by a known kneading method using a three-roll, ball mill, sand mill or the like. In addition, in the case where a filler is not blended in the photosensitive resin composition as in the case of preparing a photosensitive resin composition for an etching resist, the photosensitive resin can be obtained by mixing each component in a container such as a flask. Compositions can also be prepared.

[Production of cured product of photosensitive resist ink composition for printed wiring board production comprising photosensitive resin composition and printed wiring board]
The composition of the present invention can be used for various applications such as photoresist inks, interlayer insulating materials for printed wiring boards, resists for color filters, etc., especially for printed wiring boards and laminated boards for producing printed wiring boards. It is preferably used for forming a resist pattern such as a solder resist or an etching resist by forming a layer on the substrate.

  An appropriate substrate can be used as the substrate. For example, a glass epoxy resin substrate, a flexible substrate made of a polyimide substrate or the like, or a printed wiring board formed from these substrates can be used.

  A method for forming a resist pattern on a substrate using the composition according to the present invention is not particularly limited, and the most general method is exemplified as follows.

  For example, the composition prepared as a resist ink is applied to the substrate by dipping, spraying, spin coater, bar coater, roll coater, curtain coater, screen printing or the like, and then (H) component (diluent). In order to volatilize the organic solvent, for example, preliminary drying is performed at 60 to 120 ° C. to form a preliminary drying coating film.

  Next, directly or indirectly apply the negative mask on which the pattern has been drawn to the surface of the pre-dried film, and use a chemical lamp, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, etc. After irradiating with ultraviolet rays, a pattern is formed by development. And when (G) component (polyfunctional epoxy compound) is mix | blended, the film strength, hardness, and chemical resistance of a resist are further hardened by heating for about 30 to 90 minutes, for example at 120-180 degreeC. It is possible to improve various properties such as property.

  An appropriate organic solvent can be used as the developer used in the development step. In particular, when the component (A) has alkali solubility, an alkaline solution can be used as the developer. Examples of the alkaline solution include an aqueous sodium carbonate solution and an aqueous potassium carbonate solution. As the solvent of the alkaline solution, water or a mixture of water and an alcohol-based hydrophilic organic solvent can be used.

  The present invention will be described below based on examples, but the present invention is not limited thereto. Note that “parts” and “%” used below are based on mass unless otherwise specified.

  The “number average molecular weight”, “weight average molecular weight”, and “dispersion degree” are measured by GPC based on the following measurement conditions.

  A THF solution was prepared so that the sample obtained in each of the following synthesis examples had a solid content of 10 mg / mL, and each sample was measured at an injection amount of 100 μL.

(Measurement condition)
GPC measuring device: SHODEX SYSTEM 11 manufactured by Showa Denko KK
Column: 4 series of SHODEX KF-800P, KF-805, KF-803 and KF-801 Moving layer: THF
Flow rate: 1 mL / min Column temperature: 45 ° C
Detector: RI
Conversion: Polystyrene [Synthesis of alkali-soluble resins]
Base resins were synthesized as in Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 to 7 below.

[Synthesis Example 1]
As a reaction vessel, a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer was used, and 6.3 parts of iodine, ABN-V (2,2′-azobis) was added to this reaction vessel. (2,4-dimethylvaleronitrile)) 12.4 parts, DPM (diphenylmethane) 3.2 parts, PGMAC (propylene glycol monomethyl acetate) 100 parts, GMA (glycidyl methacrylate) 70 parts, MMA (methyl methacrylate) 30 parts In addition, the inside of the reactor was purged with nitrogen. Then, it heated at 75 degreeC under nitrogen stream for 3 hours, and while producing | generating the dormant seed | species in-situ, the living radical polymerization by RTCP polymerization method was performed.

  The number average molecular weight Mn, the weight average molecular weight Mw and the degree of dispersion Mw / Mn of the obtained polymer are as shown in the column of “Intermediate properties” in Table 1.

  After stopping the supply of nitrogen stream to the reaction vessel, 0.1 parts of HQ (hydroquinone), 37 parts of acrylic acid and 0.3 part of DMBA (dimethylbenzylamine) were added to this reaction vessel and added at 100 ° C. for 10 hours. Reaction was performed, and then 38 parts of THPA (tetrahydrophthalic anhydride) was added and reacted at 100 ° C. for 3 hours. This obtained the solution (alkali-soluble resin (A-1) solution) whose solid content of alkali-soluble resin is 66%.

  The number average molecular weight Mn, the weight average molecular weight Mw, the degree of dispersion Mw / Mn, and the acid value of this alkali-soluble resin (A-1) are as shown in the “Product Properties” column of Table 1.

[Synthesis Examples 2 to 5]
In Synthesis Example 1, the amounts of raw material components used were changed as shown in Table 1. Other than that was carried out similarly to the synthesis example 1, and obtained the solution (alkali-soluble resin (A-2)-(A-5) solution) of the alkali-soluble resin which has the intermediate body characteristic shown in Table 1, and a product characteristic.

[Synthesis Example 6]
In Synthesis Example 1, NIS (N-iodosuccinimide) was used instead of DPM, and the amounts of raw material components were changed as shown in Table 1. Other than that was carried out similarly to the synthesis example 1, and obtained the solution (alkali-soluble resin (A-6) solution) of the alkali-soluble resin which has the intermediate body characteristic shown in Table 1, and a product characteristic.

[Synthesis Example 7]
In Synthesis Example 1, diethyl phosphite was used instead of DPM, and the amounts of raw material components were changed as shown in Table 1. Otherwise in the same manner as in Synthesis Example 1, an alkali-soluble resin solution (alkali-soluble resin (A-7) solution) having intermediate characteristics and product characteristics shown in Table 1 was obtained.

[Synthesis Example 8]
In Synthesis Example 1, styrene was used instead of MMA, and the amounts of raw material components were changed as shown in Table 1. Otherwise in the same manner as in Synthesis Example 1, an alkali-soluble resin solution (alkali-soluble resin (A-8) solution) having intermediate characteristics and product characteristics shown in Table 1 was obtained.

[Synthesis Example 9]
To the reaction vessel, 1.2 parts of iodine, 2.0 parts of ABN-R (2,2′-azobisisobutyronitrile)) and 100 parts of MFDG (dipropylene glycol monomethyl ether) are added, and the inside of the reactor is nitrogen. After the substitution, a dormant species was synthesized by heating at 80 ° C. for 3 hours. Next, 35 parts of MAA (methacrylic acid), 65 parts of MMA (methyl methacrylate), V-70 (2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)) 2.9 are placed in this reaction vessel. And 0.09 part of CHD (cyclohexadiene) are added, heated to 40 ° C. under a nitrogen stream, V-70 is added by 1/8 of the initial blending amount after 2 hours and 4 hours, and reacted for 6 hours. The living radical polymerization by the RTCP polymerization method was performed.

  The number average molecular weight Mn, the weight average molecular weight Mw and the degree of dispersion Mw / Mn of the obtained polymer are as shown in the column of “Intermediate properties” in Table 1.

  After stopping the supply of nitrogen stream to the reaction vessel, 29 parts of MFDG, 0.05 part of HQ (hydroquinone), 21.3 parts of GMA (glycidyl methacrylate), 0.3 part of DMBA (dimethylbenzylamine) were added to the reaction container. And an addition reaction was carried out at 100 ° C. for 10 hours. This obtained the solution (alkali-soluble resin (A-9) solution) whose solid content of alkali-soluble resin is 50%.

  The number average molecular weight Mn, the weight average molecular weight Mw, the degree of dispersion Mw / Mn, and the acid value of the alkali-soluble resin (A-9) are as shown in the “Product Properties” column of Table 1.

[Synthesis Examples 10 and 11]
The amounts of iodine and ABN-R were changed, and the amount of solvent was adjusted so that the solid concentration was 50%. Other than that was carried out similarly to the synthesis example 9, and obtained the solution (alkali-soluble resin (A-10), (A-11) solution) of the alkali-soluble resin which has the intermediate body characteristic shown in Table 1, and a product characteristic.

[Comparative Synthesis Example 1]
To the reaction vessel, 70 parts of GMA, 30 parts of MMA, 100 parts of PGMAC, and 4 parts of ABN-V were added, heated under a nitrogen stream, and then polymerized at 65 ° C. for 6 hours while adding 4 parts of ABN-V every 1 hour. . The intermediate properties of the obtained polymer are as shown in Table 1.

  After stopping the supply of nitrogen flow to the reaction vessel, 0.1 part of HQ, 37 parts of acrylic acid and 0.3 part of DMBA were added, and an addition reaction was carried out at 100 ° C. for 10 hours, followed by addition of 38 parts of THPA at 100 ° C. It was made to react for 3 hours and the 66% solution (alkali-soluble resin (B-1) solution of alkali-soluble resin was obtained.

  The product characteristics of this alkali-soluble resin (B-1) are as shown in Table 1.

[Comparative Synthesis Examples 2 and 3]
The raw material components and the amounts used thereof were changed as shown in Table 1, and the others were the same as in Comparative Synthesis Example 1, and the alkali-soluble resin (B-2) having the molecular weight, solid content and acid value shown in Table 1 ( B-3) A solution was prepared.

[Comparative Synthesis Example 4]
To the reaction vessel, 100 parts of PGMAC, 70 parts of GMA, 30 parts of MMA, 2.72 parts of cumyl dithiobenzoate, 3.28 parts of AIBN (2,2′-azobisisobutyronitrile) are added and heated under a nitrogen stream. Living radical polymerization by reversible addition-cleavage chain transfer polymerization method (RAFT polymerization method) was performed at 70 ° C. for 4 hours to obtain a 51% solution of alkali-soluble resin (alkali-soluble resin (B-4) solution). The product characteristics of the alkali-soluble resin (B-4) are as shown in Table 1.

[Comparative Synthesis Example 5]
In a reaction vessel, 35 parts of MAA (methacrylic acid), 65 parts of MMA (methyl methacrylate), 100 parts of MFDG (dipropylene glycol monomethyl ether), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile) 2 parts were added and heated, and thereafter polymerization was carried out at 65 ° C. for 6 hours while adding 0.75 part of ABN-V four times every hour. The intermediate properties of the obtained polymer are as shown in the table.

[Comparative Synthesis Examples 6 and 7]
The amount of ABN-V was changed and the amount of solvent was adjusted so that the solid content concentration was 50%. Other than that, it had the molecular weight, solid content and acid value shown in Table 1 in the same manner as in Comparative Synthesis Example 5. An alkali-soluble resin (B-6) (B-7) solution was prepared.

[Evaluation of alkali-soluble resin]
The appearance of the resin solution obtained in each synthesis example and comparative synthesis example was visually observed to determine the degree of coloring, and the odor of this solution was sensory evaluated. The results are shown in Table 1.

  Since the alkali-soluble resin (B-4) obtained in Comparative Synthesis Example 4 exhibited a red color as shown in Table 1 and had a strong hydrogen sulfide-like odor, the following resist was not evaluated.

[Performance evaluation of liquid etching resist ink]
[Preparation of liquid etching resist ink]
By adding each component shown in Table 2 to the alkali-soluble resin solutions synthesized in the above synthesis examples and comparative synthesis examples, and stirring and mixing uniformly in the flasks, Examples 1-9, 13-15 and Comparative Examples The resist ink composition (liquid etching resist ink) for printed wiring boards of 1-3, 6-8 was obtained.

  In Table 2, “Irgacure 907” (trade name) is a photopolymerization initiator manufactured by Ciba Specialty Chemicals, and “Kayacure DETX-S” (trade name) is a photopolymerization manufactured by Nippon Kayaku Co., Ltd. It is an initiator, and “Modaflow” (trade name) is a leveling agent manufactured by Monsanto. "Aronix M-350" (trade name) is trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd., and "Victoria Blue BOH" is a dye manufactured by Hodogaya Kogyo Co., Ltd.

[Production of test piece for evaluation]
In order to confirm the performance of the printed wiring board manufactured by the liquid etching resist ink obtained in Examples 1 to 9, 13 to 15 and Comparative Examples 1 to 3 and 6 to 8, the test piece was sequentially subjected to the following steps. It was created.

<Application process>
Each liquid etching resist ink was apply | coated to the copper clad laminated board which consists of a glass epoxy base material of a 35-micrometer-thick copper foil, and the resist ink layer was formed on the substrate surface.

<Preliminary drying process>
After the coating step, preliminary drying was performed at 80 ° C. for 30 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface, and a dry coating film having a thickness of 10 μm was obtained.

<Exposure process>
Then, with a reduced pressure double-sided exposure machine (“ORC HMW-201GX” manufactured by Oak Manufacturing Co., Ltd.), a mask on which an evaluation pattern was drawn was directly applied to the dried coating film and adhered under reduced pressure, and an ultraviolet ray of 120 mJ / cm ² was applied. Irradiated to selectively expose the dried coating on the substrate surface.

<Development process>
In the dried coating film after the exposure process, the selectively non-exposed portion is removed by developing for 30 seconds using a 1% aqueous sodium carbonate solution at 30 ° C. as a developer, and then dried by exposure and curing on the substrate. A coating pattern was formed.

[Performance evaluation]
The following evaluation was performed about the test piece obtained at the said process.

<Tackiness>
The coating film (dried coating film) preliminarily dried under the above conditions is piled up so that the dried coating film surfaces are in contact with each other, and a pressure of 98 kPa (1 kg / cm ² ) is applied, and the coating film is 1 at 25 ° C. and 55% RH environment. After standing for a week, the contact between the dried coating surfaces was released. The surface of the dried coating film was observed with a 100 × microscope, and the presence or absence of contact traces such as peeling of the dried coating film or abnormal surface condition was confirmed and evaluated according to the following evaluation criteria.
X: There exists peeling in a coating film.
Δ: There is a contact mark on the surface of the coating film.
○: There is no contact mark on the coating film surface.

<Developability>
After the development process, the surface of the substrate where the non-exposed portion was removed was visually observed and evaluated according to the following evaluation criteria.
X: The state in which the color of the resist can be confirmed on the substrate surface.
Δ: The resist color cannot be confirmed on the substrate surface, but the resist residue can be confirmed.
○: Resist residue cannot be confirmed on the substrate surface.

<Remaining step stage>
The number of remaining step steps after development with an exposure test mask (manufactured by Hitachi Chemical Co., Ltd., “Step Tablet PHOTEC 21 steps”) was determined, and thereby the exposure sensitivity was evaluated.

<Resolution>
A test piece is prepared by the above-described process using a mask pattern composed of parallel lines each having a line width and a line spacing of 100 μm. Measured length. It should be noted that the closer the line width of the exposure-cured dry coating pattern is to the mask pattern, the better the resolution.

  The results are shown in Table 2. As shown in Table 2 below, when the average molecular weight was approximately the same, Examples 1 to 9, and 13 to 15 were particularly excellent in terms of resolution and tackiness.

[Performance evaluation of liquid solder resist ink]
[Preparation of liquid solder resist ink]
Alkali-soluble resins (A-1), (A-3), (A-4), (A-9) to (A-11), (B-1), (B-2) produced in the above synthesis examples ), (B-5) to (B-7) Each of the components shown in Table 3 was added to the solution and kneaded with three rolls, thereby allowing Examples 10-12, 16-18 and Comparative Examples 4, 5, 9-11 resist ink compositions for printed wiring boards (liquid solder resist inks) were obtained.

  In Table 3, “Epicron N-695” (trade name) is a cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, and “Irgacure 907” (trade name) is a light manufactured by Ciba Specialty Chemicals. It is a polymerization initiator, “Kayacure DETX-S” (trade name) is a photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd., “Modaflow” (trade name) is a leveling agent manufactured by Monsanto, and “DPHA” Is dipentaerythritol hexaacrylate.

[Production of test piece for evaluation]
In order to confirm the performance of the printed wiring boards manufactured with the liquid photo solder resist inks of Examples 10 to 12, 16 to 18 and Comparative Examples 4, 5, and 9 to 11, test pieces are prepared by sequentially performing the following steps. did.

<Application process>
Each liquid photo solder resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a 35 μm thick copper foil glass epoxy base material and a printed wiring board that has been previously etched to form a pattern, A resist ink layer was formed on the substrate surface.

<Preliminary drying process>
After the coating step, preliminary drying was performed at 80 ° C. for 20 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface, and a dried coating film having a thickness of 20 μm was obtained.

<Exposure process>
Then, with a reduced pressure double-sided exposure machine (“ORC HMW680GW” manufactured by Oak Manufacturing Co., Ltd.), a mask on which an evaluation pattern was drawn was directly applied to the dried coating film, and was closely adhered under reduced pressure, and irradiated with 200 mJ / cm ² ultraviolet rays. Selective exposure of the dried coating on the substrate surface was performed.

<Development process>
In the dried coating film after the exposure process, the selectively unexposed portion is removed by developing for 60 seconds using a 1% sodium carbonate aqueous solution at 30 ° C. as a developing solution, and then dried by exposure and curing on the substrate. A coating pattern was formed.

<Post-bake process>
The substrate on which the pattern of the exposure-cured dry coating film formed in the development process was formed was heated at 150 ° C. for 30 minutes to cure the dry coating film, thereby obtaining a test piece.

[Performance evaluation]
The following evaluation was performed about the test piece obtained at the said process.

<Tackiness>
The coating film (dried coating film) preliminarily dried under the above conditions is piled up so that the surfaces of the dried coating films are in contact with each other, and a pressure of 98 kPa (1 kg / cm ² ) is applied, and a temperature of 25 ° C. and 55% RH is applied for one week. After leaving to stand, the contact between the dried coating surfaces was released. The surface of the dried coating film was observed with a 100 × microscope, and the presence or absence of contact traces such as peeling of the dried coating film or abnormal surface condition was confirmed and evaluated according to the following evaluation criteria.
X: The state in which a contact mark is attached to the coating film surface.
(Triangle | delta): The state in which a contact mark adheres slightly on the coating-film surface.
○: No contact mark on the coating film surface.

<Developability>
After the development process, the surface of the substrate where the non-exposed part was removed was visually observed and evaluated according to the following evaluation criteria.
X: The state in which the color of the resist can be confirmed on the substrate surface.
Δ: The resist color cannot be confirmed on the substrate surface, but the resist residue can be confirmed.
○: Resist residue cannot be confirmed on the substrate surface.

<Remaining step stage>
The number of remaining step steps after development with an exposure test mask (manufactured by Hitachi Chemical Co., Ltd., “Step Tablet PHOTEC 21 steps”) was determined, and thereby the exposure sensitivity was evaluated.

<Resolution>
A test piece is prepared by the above-described process using a mask pattern composed of parallel lines each having a line width and a line spacing of 100 μm. Measured length. It should be noted that the closer the line width of the exposure-cured dry coating pattern is to the mask pattern, the better the resolution.

<Solder heat resistance>
After applying a water-soluble flux (LONCO 3355-11, manufactured by London Chemical Co., Ltd.) to the test piece, the test piece was immersed in a molten solder bath at 260 ° C. for 15 seconds and then washed with water. This cycle was performed 5 times. Thereafter, the degree of surface whitening of the exposure-cured dry coating film was observed. Moreover, the cellophane adhesive tape peeling test by the cross cut was performed based on JIS D0202 with respect to this dry coating film, and the change of the adhesion state was observed.

The evaluation method of surface whitening is as follows.
X: Remarkably whitened.
Δ: Slight whitening was observed.
○: No abnormality occurred.

Moreover, the evaluation method of adhesiveness is as follows.
X: Resist swelling or peeling occurred without performing a cross-cut test.
(Triangle | delta): Partial peeling occurred in the crosscut part at the time of tape peeling.
○: No peeling of the crosscut portion occurred.

<Pencil hardness>
The pencil hardness of the exposure-cured dry coating film was measured and evaluated according to JIS K5600.

  The above results are shown in Table 3.

[Iodine removal treatment]
(Preparation of polymer powder (A-5b) and (A-5c) by precipitation purification)
In Synthesis Example 5, after performing living radical polymerization by the RTCP polymerization method, a solvent at the time of polymerization was added to the solution after the reaction to dilute it twice to obtain a diluted solution (A-5a). The color of this diluted solution (A-5a) was pale yellow.

  The diluted solution (A-5a) was divided into two, and one of the diluted solutions (A-5a) was subjected to heat treatment with stirring at 110 ° C. for 2 hours. Thereby, the color of the liquid changed to brown. When the heat-treated liquid was passed through an activated alumina column, it became colorless. This liquid was poured into a large amount of methanol, and the polymer was precipitated and dried to obtain a white polymer powder (A-5b).

  The other diluted solution (A-5a) was poured into a large amount of methanol without being subjected to heat treatment and alumina treatment, and the polymer was precipitated and dried to obtain a white polymer powder (A-5c). .

(Preparation of polymer powder (A-9b) and (A-9c) by precipitation purification)
In Synthesis Example 9, after performing living radical polymerization by the RTCP polymerization method, a solvent during polymerization was added to the solution after the reaction to dilute it twice to obtain a diluted solution (A-9a). The color of this diluted solution (A-9a) was pale yellow.

  This diluted solution (A-9a) was divided into two, and one of the diluted solutions (A-9a) was subjected to heat treatment with stirring at 110 ° C. for 2 hours. Thereby, the color of the liquid changed to brown. When the heat-treated liquid was passed through an activated alumina column, it became colorless. This liquid was poured into a large amount of water, and the polymer was precipitated and dried to obtain a white polymer powder (A-9b).

  The other diluted solution (A-9a) was poured into a large amount of methanol without being subjected to heat treatment and alumina treatment, and the polymer was precipitated and dried to obtain a white polymer powder (A-9c). .

(Evaluation of polymer powder)
When the content of iodine was examined by elemental analysis for each polymer powder, as shown in Table 4 below, polymer powders (A-5b) and (A-) obtained from the diluted solution after the heat treatment and alumina treatment were used. No iodine was detected from 9b), and it was confirmed that iodine was completely removed. On the other hand, from the polymer powders (A-5c) and (A-9c) obtained from the diluted solution not subjected to the heat treatment, the polymer powder (A-5c) is 0.36% (theoretical value: 1. 0%) and 0.43% (theoretical value 1.2%) of iodine were detected in the polymer powder (A-9c). The reason why the detected amount of iodine is lower than the theoretical value is presumed to be that a part of iodine was removed during precipitation purification using methanol.

  In addition, the number of the polymers in the diluents (A-5a) and (A-9a) and the polymer powders (A-5b), (A-5c), (A-9b), and (A-9c) The results of measuring the average molecular weight Mn, the weight average molecular weight Mw, and the degree of dispersion Mw / Mn are shown in Table 4 below. The polymer powders (A-5b), (A-5c), (A-9b), and (A-9c) are more dispersive than the polymers in the diluted solutions (A-5a) and (A-9a). However, this is considered to be because some of the low molecular weight oligomer components were removed without precipitation by precipitation purification.

(Resist ink evaluation)
The components shown in Table 5 below were added to the reaction vessel and reacted at 100 ° C. for 3 hours. This obtained alkali-soluble resin (A-12) and (A-13) solution.

[Performance evaluation of liquid etching resist ink]
Each component shown in Table 6 was added to each of the alkali-soluble resins (A-12) and (A-13) synthesized in the above synthesis example, and the mixture was stirred and mixed uniformly in the flasks, thereby giving Examples 19 and 20 A resist ink composition for a printed wiring board (liquid etching resist ink) was obtained.

  This liquid etching resist ink was subjected to the same evaluation test as described above. The results are shown in Table 6.

[Performance evaluation of liquid solder resist ink]
The printed wirings of Examples 21 and 22 were prepared by adding the components shown in Table 7 to the alkali-soluble resin (A-12) and (A-13) solution produced in the above synthesis example and kneading them with three rolls. A resist ink composition for a plate (liquid solder resist ink) was obtained.

  This liquid solder resist ink was subjected to the same evaluation test as described above. The results are shown in Table 7.

  As described above, a solution having a solid content of 50% was prepared from the polymer powder from which iodine was removed, and liquid etching resist ink and liquid solder resist ink were prepared and evaluated. As a result, iodine was not removed. The result was equal to or better than the case.

  The photosensitive resin composition according to the present invention is particularly suitable for a photosensitive resist ink composition for producing a printed wiring board for forming a solder resist or an etching resist. It can be suitably used to form an interlayer insulating layer, a color resist for producing a color filter, a black matrix for producing a color filter, a baking paste for producing a plasma display panel, and the like.

Claims (16)

A method for producing a photosensitive resist ink composition for producing a printed wiring board comprising a photosensitive resin composition containing the following component (A) , comprising a step of adjusting a polymer by a reversible transfer catalytic polymerization method A method for producing a photosensitive resist ink composition for producing a printed wiring board characterized by:
(A) partial plastid is 1.8 or less of the polymer, of the resin obtained by modifying this polymer, a resin composed of at least one. Wherein the printed circuit board for producing photosensitive resist ink composition, the following component (B) and (C) a printed wiring board for producing photosensitive resist ink composition according to claim 1, characterized in Rukoto is contained component Manufacturing method of
(B) Photopolymerizable monomer (C) Photopolymerization initiator. On the printed wiring board for producing photosensitive resist ink composition, is contained below the component (C), the component (A) the photosensitive printed wiring board manufacturing according to claim 1, characterized in that it comprises a photosensitive Method for producing a photosensitive resist ink composition;
(C) Photopolymerization initiator. The said (A) component is alkali-soluble resin, The manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claim 1 thru | or 3 characterized by the above-mentioned. The said (A) component contains resin which has a carboxyl group in a side chain, The manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claim 1 thru | or 4 characterized by the above-mentioned. The said (A) component contains resin which has an ethylenic double bond in a side chain, The photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claim 1 thru | or 5 characterized by the above-mentioned . Manufacturing method . Ri by the reversible transfer catalyst polymerization process, by adjusting the polymer having a carboxyl group in the side chain (A1), a portion of the carboxyl group, at least one carboxyl and at least one ethylenic double bond in the molecule modified by reaction with a compound having a reactive groups which can react with group (d), any one of claims 1 to 6 thereby resulting resin is characterized in that is contained in the component (a) The manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in a term. Ri by the reversible transfer catalyst polymerization process, by adjusting the polymer having an epoxy group in the side chain, a part or all of the epoxy groups is reacted with a monocarboxylic acid, saturated or unsaturated (e), further wherein the reaction polybasic acid anhydride to a portion of the resulting hydroxyl group (f) modified by reaction with, thereby the resulting resin of claims 1 to 7, characterized in that to be contained in the component (a) The manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claims. In the reversible transfer catalytic polymerization method, a catalyst compound having at least one central element selected from germanium, tin, antimony, phosphorus, nitrogen, oxygen, and carbon and at least one halogen bonded to the central element is used. The manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claims 1 thru | or 8 characterized by these. In the reversible transfer catalytic polymerization method, a compound having at least one hydroxyl group bonded to carbon, silicon, nitrogen or phosphorus is used as a catalyst precursor corresponding to a catalyst compound having oxygen as a central element. Item 10. A method for producing a photosensitive resist ink composition for producing a printed wiring board according to Item 9. The photosensitive resist ink composition for producing a printed wiring board according to claim 9, wherein in the reversible transfer catalytic polymerization method, a carbon compound is used as a catalyst precursor corresponding to a catalyst compound having carbon as a central element. Manufacturing method . In the reversible transfer catalytic polymerization method, iodine and an azo compound are added to the reaction system before the start of polymerization, and an organic halide generated by the in-situ reaction is used as a dormant species. A method for producing a photosensitive resist ink composition for producing a printed wiring board according to claim 1 . On the printed wiring board for producing photosensitive resist ink composition, the following (G) according to claim 1 to 12 or a printed wiring board for producing a photosensitive resist ink according to one of characterized Rukoto is contained component A method for producing the composition;
(G) A polyfunctional epoxy compound. On the printed wiring board for producing photosensitive resist ink composition, the following (H) according to claim 1 to 13 or a printed wiring board for producing a photosensitive resist ink according to one of characterized Rukoto is contained component A method for producing the composition;
(H) Diluent. The photosensitive resist ink composition for printed wiring board manufacture is manufactured with the manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claims 1 thru | or 14 , This printed wiring board manufacture A method for producing a cured product, comprising curing and forming a photosensitive resist ink composition on a substrate. The photosensitive resist ink composition for printed wiring board manufacture is manufactured with the manufacturing method of the photosensitive resist ink composition for printed wiring board manufacture as described in any one of Claims 1 thru | or 14 , This printed wiring board manufacture A method for producing a printed wiring board, comprising curing and forming a photosensitive resist ink composition on a substrate.