JP6530281B2 - Active energy ray curable composition for photoresist - Google Patents

Description

  The present invention relates to an active energy ray curable composition for photoresist.

  In recent years, in forming resist patterns of various printed circuit boards, with the densification of wiring patterns, finer and more precise pattern formation is required, and improvement in resolution and dimensional accuracy is required. In the formation of such a resist pattern, a composition containing an ultraviolet-curable resin obtained by reacting a novolac epoxy acrylate with a polybasic acid anhydride (Patent Document 1), a glycidyl (meth) acrylate, and a co-polymer with this A composition comprising a resin obtainable from another polymerizable ethylenically unsaturated monomer, (meth) acrylic acid, and a saturated or unsaturated polybasic acid anhydride (Patent Document 2) has been used. In addition, since it is necessary to obtain a uniform film thickness when applying these compositions (photoresist ink) to a board | substrate, these compositions usually contain the organic solvent.

  In general, the photoresist ink is applied onto the substrate using coating means such as spraying, spin coating, roll coating, and screen printing and then heated to volatilize the organic solvent. In addition, this process is generally called preheating. After that, a photomask on which a pattern is drawn is attached on a coating film, and an active energy ray is irradiated using a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED lamp or the like, and a pattern is formed by development with an alkaline aqueous solution. And the coating film in which the resist pattern was formed can be obtained by thermosetting the reactive group which remains to a coating film.

  By performing the above-described preheating to volatilize the organic solvent, the adhesiveness of the coating film before curing by active energy rays can be reduced, so that sticking and peeling off of the photomask become easy. However, when the volatilization of the organic solvent by preheating is insufficient, adhesion of the coating film is high and adhesion and peeling off of the photomask are difficult, and radicals in the resin generated at the time of curing by active energy rays However, since the organic solvent is trapped by the remaining organic solvent, the curing reaction does not proceed sufficiently, causing a decrease in developability and a decrease in resolution. Therefore, at the time of preheating, in order to avoid the remaining of the solvent, a method of increasing the heating temperature or a method of prolonging the heating time has been adopted.

Japanese Patent Application Laid-Open No. 61-243869 Patent No. 3580429 gazette

  However, when a composition containing a resin having a reactive group such as (meth) acryloyl group or carboxyl group is heated at the preheating stage, these reactive groups are activated to cause a curing reaction, and thus, the alkali developability is obtained. It leads to a drop and a drop in resolution. In addition, since it was necessary to consider the heat resistance of the substrate to which the composition is applied, it was not easy to adjust the conditions of temperature and time of preheating. In order to solve such a problem, a composition capable of maintaining high development sensitivity regardless of the preheating conditions (heating and drying conditions) has been desired.

  Therefore, the object of the present invention is that the curing reaction does not proceed even under a wide range of heating and drying conditions, and in the subsequent curing reaction by the irradiation of active energy rays, it has excellent curability, so that the active energy for photoresist excellent in development sensitivity It is providing a radiation curable composition.

  The inventors of the present invention have found that an active energy ray-curable resin for a photoresist contains an acrylic copolymer resin (A) having a specific structure, an acrylic copolymer resin (B) having a specific structure, and a photopolymerization initiator (C). The composition is excellent in stability during preheating (heating and drying), the curing reaction does not proceed, the coating film can be sufficiently dried, and peeling of the photomask after preheating becomes easy. Furthermore, in the hardening reaction by irradiation of the active energy ray after that, since it has favorable hardenability, it discovered that it was excellent in development sensitivity, and completed this invention.

That is, the present invention provides the following active energy ray curable composition for photoresist.
[1] An active energy ray-curable composition for a photoresist, which comprises an acrylic copolymer resin (A), an acrylic copolymer resin (B), and a photopolymerization initiator (C),
The acrylic copolymer resin (A) is an acrylic copolymer resin having a (meth) acryloyl group and a carboxyl group in a side chain,
The acrylic copolymer resin (B) has a (meth) acryloyl group and a carboxyl group in a side chain, and it is an acrylic copolymer resin having a resin skeleton different from that of the above acrylic copolymer resin (A). Active energy ray curable composition for resists.
[2] The active energy ray for photoresist according to [1], wherein the acrylic copolymer resin (A) is an acrylic copolymer resin containing a monomer unit having both a (meth) acryloyl group and a carboxyl group in a side chain. Curable composition.
[3] The content of monomer units having both a (meth) acryloyl group and a carboxyl group in the side chain is 15 to 70% by weight based on the total amount of monomer units constituting the acrylic copolymer resin (A) [2 ] The active energy ray curable composition for photoresists as described in these.
[4] The acrylic copolymer resin (B) has a (meth) acryloyl group in the side chain and has no carboxyl group, and has a carboxyl group in the side chain, and (meth) acryloyl group The active energy ray curable composition for photoresists as described in any one of [1] to [3], which is an acrylic copolymer resin containing a monomer unit having no.
[5] In any one of [1] to [4], the acrylic copolymer resin (A) is an acrylic copolymer resin having at least a carboxyl group derived from polybasic acid anhydride in the side chain. The active energy ray curable composition for photoresists as described.
[6] The activity for a photoresist according to any one of [1] to [5], wherein the resin acid value of the acrylic copolymer resin (A) is 30 to 200 mg KOH / g, and the weight average molecular weight is 5000 to 100000. Energy ray curable composition.
[7] The activity for a photoresist according to any one of [1] to [6], wherein the resin acid value of the acrylic copolymer resin (B) is 20 to 200 mg KOH / g, and the weight average molecular weight is 5,000 to 30,000. Energy ray curable composition.
[8] The active energy ray curable composition for photoresist according to any one of [1] to [7], wherein the resin acid value (X) obtained by the following formula is 40 to 105 mg KOH / g.
Resin acid number (X) (mg KOH / g) = (resin acid number of acrylic copolymer resin (A)) × a + (resin acid number of acrylic copolymer resin (B)) × b
a = content of acrylic copolymer resin (A) (g) / sum of content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g)
b = total content of acrylic copolymer resin (B) (g) / total content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g)
[9] A cured product of the active energy ray-curable composition for photoresist according to any one of [1] to [8].

  The active energy ray-curable composition for photoresists of the present invention uses at least two acrylic copolymer resins having (meth) acryloyl groups and carboxyl groups in the side chains, which have different resin skeletons, and thus preheating ( At the time of heating and drying), the curing reaction of the resin component by heating is difficult to progress (heat stability is high), and since it has good curability at the time of curing by active energy rays, development sensitivity is good. . In particular, an acrylic copolymer having an acrylic copolymer resin containing a monomer unit having both a (meth) acryloyl group and a carboxyl group in a side chain, and an acrylic copolymer having a (meth) acryloyl group and a carboxyl group on the side chain of separate monomer units By combining the resins, although the reason is not clear, it is possible to suppress the curing at the time of heat drying while maintaining the curability by the active energy ray from the balance of reactivity between the resins.

  The present invention provides an active energy ray curing for a photoresist comprising an acrylic copolymer resin (A) having a specific structure, an acrylic copolymer resin (B) having a specific structure, and a photopolymerization initiator (C). It relates to a sex composition. The active energy ray-curable composition for a photoresist of the present invention may contain, in addition to the above components, an organic solvent described later and other components (viscosity modifiers and the like).

In addition, with the acrylic copolymer resin in this invention, the (meth) acrylic-type monomer unit (For example, the monomer unit originating in (meth) acrylic acid and (meth) acrylic acid ester) which has a carboxyl group in a side chain is essential Or a copolymer which may contain other radically polymerizable monomers as monomer units. Further, the main chain of the acrylic copolymer resin in the present specification refers to a carbon chain (a carbon chain derived from a radical polymerizable group) generated by a radical polymerization reaction (for example, an acrylic polymerization reaction) when producing the resin. The term side chain (or side chain substituent) refers to a substituent attached to the main chain. For example, in the monomer unit represented by the formula (1) described later, the carbon chain represented by -CH ₂ -C- in the parenthesis represents the main chain, and the carbon atom identical to R ¹ or R ¹ is used. The attached substituent represents a side chain (or a substituent of a side chain).

<Acrylic copolymer resin (A)>
The acrylic copolymer resin (A) in the present invention is characterized in that it is an acrylic copolymer resin having a (meth) acryloyl group and a carboxyl group in a side chain. The acrylic copolymer resin (A) is not particularly limited as long as it has the above characteristics, but an acrylic copolymer resin containing at least a monomer unit (UA1) having both a (meth) acryloyl group and a carboxyl group in a side chain Is preferred.

  The acrylic copolymer resin (A) of the present invention is a monomer having both a (meth) acryloyl group and a hydroxyl group in the side chain in addition to the monomer unit (UA1) having both a (meth) acryloyl group and a carboxyl group in the side chain. At least one monomer unit selected from the group consisting of units (UA2), monomer units having a carboxyl group in the side chain (UA3), and monomer units having a hydrocarbon group in the side chain (UA4) may be further included , Other monomer units (UA5) may be included. The above monomer units may be referred to as a monomer unit (UA1), a monomer unit (UA2), a monomer unit (UA3), a monomer unit (UA4) and a monomer unit (UA5), respectively.

The monomer unit (UA1) is not particularly limited as long as it is a monomer unit having both a (meth) acryloyl group and a carboxyl group in a side chain, and is preferably, for example, a monomer unit represented by the following formula (1).

In formula (1), R ¹ and R ² are the same or different and each independently represent a hydrogen atom or a methyl group. A ¹ is a trivalent hydrocarbon group (an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group in which two or more of these are bonded) or two or more hydrocarbon groups; Or a trivalent group bonded via two or more ester structures (-CO-O-). The total carbon number of A ¹ is, for example, 2 to 20, preferably 2 to 15, and more preferably 2 to 10. A ² represents a divalent hydrocarbon group which may have a substituent. As said bivalent hydrocarbon group, a C2-C10 bivalent hydrocarbon group, a C3-C12 alicyclic hydrocarbon group, a C6-C14 bivalent aromatic group is mentioned, for example A hydrocarbon group or a group in which two or more of these are bonded may be mentioned. As the substituent, for example, a hydrocarbon group which may have a carboxyl group or an acid anhydride structure (—CO—O—CO—); a carboxyl group or an acid anhydride structure (—CO—O—CO— A group in which one or more of a hydrocarbon group which may have one or more bonds with one or more of an ester structure (-CO-O-); a carboxyl group or an acid anhydride structure (-CO-O) A group in which one or more of a hydrocarbon group which may have —CO— and one or more of a carbonyl group (—CO—) are bonded; or a carboxyl group or an acid anhydride structure (— CO-O-CO-) 1 or 2 or more of the hydrocarbon group which may have, 1 or 2 or more of ester structure (-CO-O-), and 1 or 2 of carbonyl group (-CO-) Examples thereof include a group in which two or more are bonded. A ² may be bonded to the side chain of the same or different acrylic copolymer resin via, for example, an ester structure (—CO—O—). The total carbon number of A ² is, for example, 2 to 25, preferably 2 to 20.

Further, the monomer unit (UA1) is more preferably a monomer unit represented by the following formula (1-1) or formula (1-2).

In Formula (1-1) and Formula (1-2), R ¹ , R ² , and A ² may be the same as described above. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms). R ⁴ represents a divalent hydrocarbon having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and n represents 0 or 1. R ^{5 to} R ⁷ are the same or different and each independently represent hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. R ⁵ and R ⁶ or R ⁷ may be bonded to each other to form a ring with two adjacent carbon atoms. As said ring, a C5-C12 alicyclic (monocyclic or polycyclic) hydrocarbon etc. are mentioned.

The monomer unit (UA2) is not particularly limited as long as it is a monomer unit having both a (meth) acryloyl group and a hydroxyl group in a side chain, but a monomer unit represented by the following formula (2) is preferable, for example. It is more preferable that it is a monomer unit represented by -1) or Formula (2-2).

R ^{1 to} R ⁷ , A ¹ and n in the formulas (2), (2-1), and the formula (2-2) are the same as those of the formula (1), the formula (1-1), and the formula The same ones as described in 1-2) can be mentioned.

The monomer unit (UA3) is not particularly limited as long as it is a monomer unit having a carboxyl group in the side chain and is other than the monomer unit (UA1), for example, a monomer unit represented by the following formula (3) It can be mentioned.

In formula (3), R ⁸ is the same or different and represents a hydrogen atom or a methyl group. R ⁹ represents a divalent hydrocarbon having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and 1 represents 0 or 1.

The monomer unit (UA4) is not particularly limited as long as it is a monomer unit having a hydrocarbon group in a side chain, and examples thereof include a monomer unit represented by the following formula (4).

In formula (4), R ¹⁰ is the same or different and represents a hydrogen atom or a methyl group. R ¹¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). As said hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the group which 2 or more these couple | bonded are mentioned.

The monomer unit (UA5) is not particularly limited as long as it is a monomer unit that can form a polymer with the monomer units (UA1) to (UA4). As an example of a monomer unit (UA5), the monomer unit which has an epoxy group in the side chain represented by following formula (5) is mentioned.

In formula (5), R ¹² is the same or different and represents a hydrogen atom or a methyl group. R < ¹³ > shows a C1-C10 (preferably C1-C5) divalent hydrocarbon group. R ^{14 to} R ¹⁶ are the same or different and each independently represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. R ¹⁴ and R ¹⁵ or R ¹⁶ may be combined with each other to form a ring with two adjacent carbon atoms. As said ring, a C5-C12 alicyclic (monocyclic or polycyclic) hydrocarbon etc. are mentioned.

  The content of the monomer unit (UA1) having both a (meth) acryloyl group and a carboxyl group in the side chain is 15 to 70% by weight based on the total amount of monomer units constituting the acrylic copolymer resin (A) of the present invention It is preferably 17 to 60% by weight, more preferably 19 to 55% by weight.

  The acrylic copolymer resin (A) is preferably, for example, an acrylic copolymer resin having a carboxyl group derived from polybasic acid anhydride at least in a side chain, and is derived from a polybasic acid anhydride in a side chain It is more preferable that it is an acrylic copolymer resin having a carboxyl group and a (meth) acryloyl group derived from (meth) acrylic acid ester having (meth) acrylic acid and / or carboxyl group, and a polybasic in the side chain Carboxyl group derived from acid anhydride, (meth) acryloyl group derived from (meth) acrylic acid ester having (meth) acrylic acid and / or carboxyl group, and (meth) acrylic acid ester having an epoxy group It is more preferable that it is an acrylic copolymer resin having a hydroxyl group.

  The resin acid value of the acrylic copolymer resin (A) is not particularly limited, but is preferably 30 to 200 mg KOH / g, more preferably 40 to 100 mg KOH / g, and still more preferably 50 to 80 mg KOH / g. When the resin acid value is in the above range, the heating stability is improved, and the resolution in alkali development is improved.

  Although the weight average molecular weight of acrylic type copolymer resin (A) is not specifically limited, Preferably it is 5000-100000, More preferably, it is 7000-80,000, More preferably, it is 10000-50000. When the weight average molecular weight is in the above range, the heating stability is good, and the solubility in a solvent (such as an organic solvent) is good, so the workability is excellent.

  The content of the acrylic copolymer resin (A) is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, based on the resin content (100% by weight) in the active energy ray-curable composition for photoresists. More preferably, it is 15 to 85% by weight. The resin component refers to, for example, a curable compound such as an acrylic copolymer resin (A), an acrylic copolymer resin (B), and an epoxy resin described later, and a photopolymerization initiator (C) and an organic solvent It refers to things except for etc. When the content of the acrylic copolymer resin (A) is in the above range, the heat stability and the curability become good.

[Method for producing acrylic copolymer resin (A)]
The acrylic copolymer resin (A) can be produced, for example, by the following process.
Step A1: A step of producing an acrylic copolymer resin containing at least a monomer unit derived from a (meth) acrylic acid ester having an epoxy group by a radical polymerization reaction (acrylic polymerization reaction) Step A2: Acrylic obtained in Step A1 A step of producing an acrylic copolymer resin containing a monomer unit (UA2) by subjecting a base copolymer resin and a (meth) acrylic acid and / or a (meth) acrylic acid ester having a carboxyl group to a reaction, Step A3: A step of producing an acrylic copolymer resin containing a monomer unit (UA1) by reacting the acrylic copolymer resin obtained in step A2 with a polybasic acid anhydride

Although the model of the manufacturing method of acrylic type copolymer resin (A) is shown below, this invention is not limited at all by this model. In the following model, an acrylic copolymer resin containing at least a monomer unit represented by the formula (5) is reacted with a (meth) acrylic acid and / or a (meth) acrylic acid ester having a carboxyl group, -1) and / or after producing an acrylic copolymer resin containing a monomer unit represented by the formula (2-2), it is further reacted with a polybasic acid anhydride to obtain the formula (1-1) and / or Or it is explained that an acrylic copolymer resin containing a monomer unit represented by the formula (1-2) can be prepared. That is, the acrylic copolymer resin (A) is an acrylic copolymer resin containing at least an epoxy group in a side chain (an acrylic copolymer resin containing at least a monomer unit derived from a (meth) acrylate having an epoxy group) And an acrylic copolymer resin obtained by the reaction of a (meth) acrylic acid having (meth) acrylic acid and / or a carboxyl group, and a polybasic acid anhydride. Incidentally, R ¹ ~R ^7, A ² in the model, and n are as defined above.

(Step A1)
Step A1 is a step of producing an acrylic copolymer resin containing at least a monomer unit derived from a (meth) acrylic ester having an epoxy group by radical polymerization reaction (acrylic polymerization reaction). In addition to (meth) acrylic acid ester having an epoxy group, for example, (meth) acrylic acid ester having (meth) acrylic acid and / or carboxyl group, and (meth) acrylic acid ester having a hydrocarbon group, Furthermore, the acrylic copolymer resin may be produced by subjecting another radically polymerizable compound to a radical polymerization reaction as required. That is, an acrylic copolymer resin containing at least a monomer unit derived from a (meth) acrylic ester having an epoxy group is derived from, for example, a (meth) acrylic acid having (meth) acrylic acid and / or a carboxyl group A monomer unit, a monomer unit derived from a (meth) acrylate having a hydrocarbon group, and a monomer unit derived from another radically polymerizable compound may be included.

  The monomer unit derived from (meth) acrylic acid and / or (meth) acrylic acid ester having a carboxyl group in step A1 corresponds to the above-mentioned monomer unit (UA3), and is represented by the above-mentioned formula (3). And a monomer unit derived from a (meth) acrylate having a hydrocarbon group corresponds to the above monomer unit (UA4) and is a monomer unit represented by the above formula (4) And monomer units derived from other radically polymerizable compounds correspond to the above-mentioned monomer units (UA5). By such a process, an acrylic copolymer resin having an epoxy group in a side chain can be obtained.

  When a (meth) acrylic acid having (meth) acrylic acid and / or a carboxyl group is used in step A1, the amount thereof used is 5 to 400 with respect to 100 parts by weight of the (meth) acrylic acid ester having an epoxy group. It is preferably part by weight, more preferably 10 to 350 parts by weight, still more preferably 15 to 300 parts by weight.

  When a (meth) acrylic acid ester having a hydrocarbon group is used in step A1, the amount thereof is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester having an epoxy group, More preferably, it is 0.5 to 20 parts by weight, still more preferably 1 to 15 parts by weight.

  Although a polymerization initiator can also be used for the radical polymerization reaction (acrylic polymerization reaction) in step A1, as such a polymerization initiator, for example, diisopropyl benzene hydroperoxide of hydroperoxide, cumene hydroperoxide, t-Butyl hydroperoxide, and dicumyl peroxide of dialkyl peroxides, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane, 1,3-bis- (t-butyl) Peroxyisopropyl) -benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexyne-3, and diacyl peroxide Isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide Oxides, lauroyl peroxide, benzoyl peroxide, acetyl peroxide, and ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, and alkyl peresters t-butyl peroxy biva Rate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexaate, t-butylperoxyacetate, t-butylperoxybenzoate, and peroxydicarbonate Diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperamide Oxydicarbonates and azo compounds such as azobisisobutyronitrile, methyl 2,2-azobisisobutyrate, azobiscyanovaleronitrile, 1,1-azobis (cyclohexene-1-carbonitrile), 2,2-azobis { 2-methyl-N- (2-hydroxyethyl) -propionamide} etc. are mentioned.

  The radical polymerization reaction (acrylic polymerization reaction) is usually carried out in an organic solvent. Examples of the organic solvent used in step A1 include hydrocarbon solvents such as toluene and xylene, n-butyl acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, dimethyl glutarate, dimethyl succinate, and dimethyl adipate ester There are solvents, ketone solvents such as methyl isobutyl ketone and diisobutyl ketone, and ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol monomethyl ether acetate. Among them, it is preferable to use a high boiling point solvent such as propylene glycol monomethyl ether or the same acetate, dimethyl glutarate, dimethyl succinate or dimethyl adipate. Methyl ethyl ketone, ethyl acetate and butyl acetate can also be used if necessary. The organic solvents can be used in combination of two or more.

(Step A2)
The step A2 is a step of producing an acrylic copolymer resin by reacting the acrylic copolymer resin obtained in the step A1 with (meth) acrylic acid and / or (meth) acrylic acid ester having a carboxyl group. It is.

  By the above reaction, an acrylic copolymer resin having a (meth) acryloyl group and a hydroxyl group in the side chain is formed. Specifically, the carboxyl group of (meth) acrylic acid and / or (meth) acrylic acid ester having a carboxyl group react with the epoxy group of the acrylic copolymer resin obtained in step A1 to form an ester structure At the same time, hydroxyl groups derived from epoxy groups are formed. By such reaction, an acrylic copolymer resin containing a monomer unit having both a hydroxyl group and a (meth) acryloyl group in a side chain can be obtained. The monomer unit having both a hydroxyl group and a (meth) acryloyl group in the side chain is the monomer unit (UA2) and is exemplified by the monomer unit represented by the formula (2).

  In addition, as an organic solvent in process A2, what was demonstrated by process A1 can be used.

  The (meth) acrylic acid and / or (meth) acrylic acid ester having a carboxyl group to be reacted with the acrylic copolymer resin obtained in the step A1 is the total of the epoxy groups of the side chains in the acrylic copolymer resin. The total number of moles (total amount) of carboxyl groups in the (meth) acrylic acid and the (meth) acrylic acid ester having a carboxyl group relative to the number of moles is, for example, used in a range of 0.7 to 1.3. It is preferable to use in the range of 0.8 to 1.1, and it is further preferable to use in the range of 0.95 to 1.0. If it is less than 0.7, there is a possibility that a component not having a (meth) acryloyl group may be mixed, so it may be present as an uncured component at the time of active energy ray curing, which may lower the developability of the coating film. is there. Also, if it is larger than 1.3, free (meth) acrylic acid will be present in the system, which may cause the contamination of the substrate.

Although the double bond equivalent (g / mol) calculated by the following formula in the acrylic copolymer resin obtained in the above step A2 is not particularly limited, for example, 100 to 1000 g / mol is preferable, and more preferably 150 It is -800 g / mol, and more preferably 200-600 g / mol.
Double bond equivalent (g / mol) = molecular weight of acrylic copolymer resin / number of (meth) acryloyl groups contained in acrylic copolymer resin

(Step A3)
The step A3 is a step of producing an acrylic copolymer resin by reacting the acrylic copolymer resin obtained in the step A2 with a polybasic acid anhydride.

  In step A3, the hydroxyl group of the acrylic copolymer resin obtained in step A2 is reacted with the polybasic acid anhydride to form a carboxyl group derived from the polybasic acid anhydride in the acrylic copolymer resin. Ru. By this step, the acrylic copolymer resin (A) becomes an acrylic copolymer resin containing a monomer unit having both a (meth) acryloyl group and a carboxyl group in the side chain. The monomer unit having both a (meth) acryloyl group and a carboxyl group in the side chain is the monomer unit (UA1) and is exemplified by the monomer unit represented by the formula (1).

  The use amount (total amount) of the polybasic acid anhydride used in step A3 is preferably 1 to 80 parts by weight, more preferably 4 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer resin obtained in step A2. It is a part by weight, more preferably 6 to 40 parts by weight.

  A reaction accelerator can be used in step A3. The reaction accelerator is a compound having a function of accelerating the reaction rate when a compound having an epoxy group (oxiranyl group) reacts with a polybasic acid anhydride. As the reaction accelerator, known or conventional ones can be used, and it is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (eg, phenol salt, octyl) Acid salts, p-toluenesulfonates, formates, tetraphenylborates, etc .; 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or salts thereof (eg, phenol salts, octylates) P-toluenesulfonate, formate, tetraphenylborate and the like); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and N, N-dimethylcyclohexylamine; Imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphoric acid S Phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometal salts such as zinc octylate, tin octylate and zinc stearate; aluminum acetylacetone Metal chelates, such as a complex, etc. are mentioned.

  In addition, as an organic solvent which can be used for process A3, what was demonstrated in process A1 is mentioned.

  The (meth) acrylic acid ester having an epoxy group is not particularly limited as long as it is an acrylic acid ester having an epoxy group in the molecule, and, for example, oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methyl ester Glycidyl (meth) acrylate, 2-ethyl glycidyl (meth) acrylate, 2-oxiranylethyl (meth) acrylate, 2-glycidyl oxyethyl (meth) acrylate, 3-glycidyl oxypropyl (meth) acrylate, glycidyl oxyphenyl ( Examples thereof include (meth) acrylic acid ester derivatives such as meta) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

  The (meth) acrylic acid ester having a carboxyl group is not particularly limited as long as it is an acrylic acid ester having a carboxyl group in the molecule, but, for example, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrate Hydrophthalic acid, 2-acryloyloxyethyl-phthalic acid and the like can be mentioned.

  The (meth) acrylic acid ester having a hydrocarbon group is not particularly limited as long as it is a (meth) acrylic acid ester having a hydrocarbon group in the molecule, but, for example, methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) Linear or branched hydrocarbon groups such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc. Have ( Ta) acrylic acid ester; (meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclohexyl (meth) acrylate; and (meth) acrylic acid ester having an aromatic hydrocarbon group such as benzyl (meth) acrylate Etc.

  The other radical polymerizable compound is not particularly limited as long as it is a compound having radical polymerization property, and examples thereof include (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide and N- Acrylamide compounds such as tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide and diacetone (meth) acrylamide; radically polymerizable groups such as vinyl group, vinyl ether group, vinyl aryl group, and vinyloxycarbonyl group And compounds having one or more in one molecule; and vinyl pyrrolidone, acrylonitrile and the like.

  Examples of the polybasic acid anhydride include, but are not limited to, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, methyl, for example. Dibasic acid anhydrides such as tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid Acid anhydrides, mixtures of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, and acid anhydrides such as ethylene glycol bistrimellitic anhydride (ethylene glycol bisanhydro trimellitate) can be mentioned.

  As a commercial item of polybasic acid anhydride, for example, RIKACID MH-700F (4-methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture: Shin Nippon Rika Co., Ltd. product), RIKACID TMEG-500 (ethylene glycol bis) Anhydrotrimellitate, Shin Nippon Rika Co., Ltd., RIKASHID TMEG-200 (ethylene glycol bisanhydrotrimellitate: Shin Nippon Chemical Co., Ltd.), and trimellitic anhydride (trimellitic anhydride: Mitsubishi Gas Chemical Co., Ltd.) can be used.

  The acrylic copolymer resin (A) can be produced by appropriately using known reactions in addition to the above production method.

<Acrylic copolymer resin (B)>
The acrylic copolymer resin (B) of the present invention is an acrylic copolymer resin having a (meth) acryloyl group and a carboxyl group in a side chain and having a resin skeleton different from that of the acrylic copolymer resin (A). It is characterized by The difference in resin skeleton means that the monomer unit constituting the acrylic copolymer resin (A) and the monomer unit constituting the acrylic copolymer resin (B) do not completely coincide with each other.

  The monomer unit contained in the acrylic copolymer resin (B) is not particularly limited, but, for example, a monomer unit having a (meth) acryloyl group in a side chain and having no carboxyl group, and a carboxyl group in a side chain And monomer units not having a (meth) acryloyl group, and it is preferable to simultaneously contain these monomer units. That is, it is preferable that acrylic copolymer resin (B) is an acrylic copolymer resin which has a (meth) acryloyl group and a carboxyl group in the side chain of a separate monomer unit. In addition to the above monomer units, monomer units having a hydrocarbon group in the side chain, and other monomer units may be contained. In addition, what was illustrated by the term of acrylic type copolymer resin (A) is mentioned to the monomer unit which has the said hydrocarbon group, and another monomer unit. As one of the differences between the resin skeletons of the acrylic copolymer resin (A) and the acrylic copolymer resin (B), for example, the presence or absence of the above-mentioned monomer unit (UA1) can be mentioned.

  The acrylic copolymer resin (B) is not particularly limited as long as it has the above-mentioned characteristics, but, for example, it has a (meth) acryloyl group derived from a (meth) acrylic acid ester having an epoxy group in the side chain It is preferable that it is an acrylic copolymer resin, (meth) acryloyl group and hydroxyl group derived from (meth) acrylic acid ester having epoxy group, and (meth) acrylic acid having (meth) acrylic acid and / or carboxyl group It is more preferable that it is an acrylic copolymer resin having a carboxyl group derived from an ester in a side chain. The acrylic copolymer resin (B) may further have a side chain derived from a (meth) acrylic acid ester having a hydrocarbon group or a side chain derived from another radically polymerizable compound. In addition, the (meth) acrylic acid ester having an epoxy group, the (meth) acrylic acid ester having a carboxyl group, the (meth) acrylic acid ester having a hydrocarbon group, and other radically polymerizable compounds are acrylic resins. Those exemplified in the section of the copolymer resin (A) can be mentioned.

  The acrylic copolymer resin (B) of the present invention is an acrylic copolymer resin obtained by the reaction of an acrylic copolymer having a carboxyl group in a side chain and a (meth) acrylic acid ester having an epoxy group, It is also good.

  The resin acid value of the acrylic copolymer resin (B) is not particularly limited, but is preferably 20 to 200 mg KOH / g, more preferably 25 to 150 mg KOH / g, and still more preferably 30 to 120 mg KOH / g. When the resin acid value is in the above range, the heating stability is improved, and the resolution at the time of alkali development is improved.

  Although the weight average molecular weight of acrylic type copolymer resin (B) is not specifically limited, Preferably it is 5000-30000, More preferably, it is 5000-25000, More preferably, it is 800-15000. When the weight average molecular weight is in the above range, the heat resistance is good, and since the solubility in a solvent (organic solvent etc.) is good, the workability is excellent.

  The content of the acrylic copolymer resin (B) is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, based on the resin content (100% by weight) in the active energy ray-curable composition for photoresists. More preferably, it is 15 to 85% by weight. The resin content is as described above. When the content of the acrylic copolymer resin (B) is in the above range, the heat stability and the curability become good.

  The ratio (parts by weight) of the acrylic copolymer resin (A) and the acrylic copolymer resin (B) contained in the active energy ray-curable composition for photoresist is the former: the latter = 5 to 95: 95 to 5 Is preferably, and more preferably 10 to 90: 90 to 10.

  As a commercial item of acrylic copolymer resin (B), cyclomer P (ACA200) [weight average molecular weight 15000 to 18000, resin acid value made by Daicel Ornex Co., Ltd., whose basic skeleton is composed of an acrylic copolymer] 105 to 125 mg KOH / g, cyclomer P (ACA 230 AA) [weight average molecular weight 10000 to 16000, resin acid value 33 to 47 mg KOH / g], cyclomer P (ACA 200 M) [weight average molecular weight 10000 to 13000, resin acid value 105 to 5 125 mg KOH / g], cyclomer P (ACAZ 250) [weight average molecular weight 9000 to 12000, resin acid value 70 to 80 mg KOH / g], cyclomer P (ACA 320) [weight average molecular weight 20000 to 27000, resin acid value 120 to 140 mg KOH / g] It can be used.

<Photoinitiator (C)>
As the photopolymerization initiator (C), for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2) -Propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, Benzyl dimethyl ketal, benzofu Non, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2- Chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthiooxane Song, 2,4,6-trimethyl benzoyl diphenyl phosphite oxide, methylphenyl glyoxylate, benzyl, camphor quinone etc. are mentioned.

  The content of the photopolymerization initiator (C) relative to the resin content (100 parts by weight) in the active energy ray-curable composition for photoresists is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 It is a part by weight, more preferably 0.5 to 3 parts by weight. The resin content is as described above.

  The content of the photopolymerization initiator (C) relative to the active energy ray curable composition (100% by weight) for photoresist is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight .

<Organic solvent>
An organic solvent can be used for the active energy ray curable composition for photoresists of the present invention for the purpose of obtaining a uniform film thickness when the composition is applied to a substrate, and for the purpose of adjusting viscosity. As the organic solvent, known or commonly used organic solvents can be used, and although not particularly limited, glycol solvents, ester solvents, ketone solvents, mixed solvents containing these, and the like can be mentioned. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and mixtures thereof are preferable. In the composition of the present invention, one kind of organic solvent can be used alone, or two or more kinds can be used in combination. Further, the content (blending amount) of the organic solvent in the composition of the present invention is not particularly limited, but for example, 10 to 10 parts by weight of the total content of the acrylic copolymer resins (A) and (B) The amount is 5000 parts by weight, preferably 20 to 3000 parts by weight, and more preferably 30 to 2000 parts by weight.

<Other ingredients>
The active energy ray-curable composition for photoresists of the present invention comprises, in addition to the components described above, resins such as epoxy resins and acrylic resins other than acrylic copolymer resins (A) and (B), and colorants (for example, It may further contain other components such as dyes). The content (blending amount) of these other components is not particularly limited, and can be appropriately set from well-known and commonly used amounts.

  As described above, the active energy ray curable composition for photoresist of the present invention may also be compounded with an epoxy resin to adjust the hardness of the coating. Such an epoxy resin is not particularly limited. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A-novolak epoxy resin, sorbitol polyglycidyl ether, Sorbitan polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, neopentyl polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,6-hexanediol polyglycidyl ether , Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Polyols, polyglycidyl ether compounds such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, and adipic acid cyglycidyl ester, o- Glycidyl ester compounds such as phthalic acid diglycidyl ester, N-glycidyl type epoxy resin, or alicyclic epoxy resin (for example, "EHPE-3150" manufactured by Daicel Co., Ltd.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene- A phenol type epoxy resin, a naphthalene type epoxy resin, etc. are mentioned. Among these, aromatic epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and bisphenol A novolac epoxy resin are particularly preferable. In addition, these content (compounding quantity) is not specifically limited, It can set suitably from well-known and usual quantity.

  The active energy ray-curable composition for a photoresist of the present invention can be obtained by blending and mixing the components constituting the composition by a known or conventional method. For example, an acrylic copolymer resin (A) and an acrylic copolymer resin (B) are dissolved in an organic solvent (solvent for resist), and a solution (polymer solution for photoresist) obtained is a photopolymerization initiator (C). The composition of the present invention is obtained by the method of adding. Further, the acrylic copolymer resin (A) dissolved in an organic solvent (solvent for resist) and the acrylic copolymer resin (B) dissolved in organic solvent (solvent for resist) are mixed at a predetermined ratio, The composition of this invention is obtained by the method of adding a photoinitiator (C) to the obtained solution.

The active energy ray-curable composition for photoresists of the present invention preferably has a resin acid value (X) of 40 to 105 mg KOH / g, more preferably 42 to 104 mg KOH / g, and further preferably 40 to 105 mg KOH / g, Preferably it is 44-103 mgKOH / g. When the resin acid value (X) is in the above range, the heating stability is improved, and the resolution in alkali development is improved.
Resin acid number (X) (mg KOH / g) = (resin acid number of acrylic copolymer resin (A)) × a + (resin acid number of acrylic copolymer resin (B)) × b
a = content of acrylic copolymer resin (A) (g) / sum of content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g)
b = total content of acrylic copolymer resin (B) (g) / total content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g)

  The active energy ray curable composition for photoresists of the present invention can be cured using active energy rays and the like to obtain a cured product. For example, the pattern can be formed by applying the composition onto a substrate or substrate and then curing (drying) and then developing. More specifically, the active energy ray curable composition for photoresist of the present invention is applied onto a substrate or a substrate and dried to form a coating film (resist film), and then the above-mentioned composition is applied through a predetermined mask. The fine pattern can be formed with high accuracy by curing (for example, exposing) the coating film to form a latent image pattern and then developing. By forming a pattern in such a process, a semiconductor can be manufactured with high accuracy and high efficiency.

  As the above substrate or substrate, any known or commonly used substrate or substrate can be used, and it is not particularly limited, but silicon wafer, metal substrate (substrate), plastic substrate (substrate), glass substrate (substrate) And ceramic base materials (substrates). Moreover, application of the composition (photosensitive resin composition) of the present invention can be performed using a conventional application means such as a spin coater, dip coater, roller coater or the like. Although the thickness of the said coating film is not specifically limited, 0.01-200 micrometers is preferable, More preferably, it is 0.02-150 micrometers.

For the exposure of the coating film, light beams of various wavelengths (for example, ultraviolet rays, X-rays, etc.) can be used, and there is no particular limitation, but for semiconductor resists, g-rays, i-rays, excimer lasers (eg, XeCl, etc.) are usually used. KrF, KrCl, ArF, ArCl, etc.), extreme ultraviolet light (EUV) etc. can be used. The composition (resist composition, composition for lithography) of the present invention is particularly suitable for exposure to far ultraviolet light having a wavelength of 220 nm or less. The exposure energy is not particularly limited, but is preferably 1 to 1000 mJ / cm ² , and more preferably ² to 100 mJ / cm ² .

  The present invention will be described in more detail based on examples given below, but the present invention is in no way limited by these examples.

Synthesis Examples 1 to 9 (Synthesis of Acrylic Copolymer Resin (A))
Synthesis Example 1
In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirrer, 2000 g of diethylene glycol monomethyl ether acetate was charged, and the internal temperature was set to 110 ° C. There, 1034 g of glycidyl methacrylate, 39 g of methacrylic acid, 359 g of butyl methacrylate, 27 g of 2,2-azobis (2-methylbutyronitrile) as a polymerization initiator [Dupont, trade name: VAZO 67] The mixed solution at normal temperature was added dropwise over 4 hours. Next, 5 g of VAZO 67 was added three times every one hour. Furthermore, in order to eliminate the polymerization initiator, the internal temperature was raised to 120 ° C. and then heated for 3 hours. Thereafter, the temperature was lowered to 105 ° C., and 5 g of triphenylphosphine, 2 g of phenothiazine and 4 g of dibutyl hydroxytoluene were added as a stabilizer. Then 5 g of benzyldimethylamine were added. Thereafter, 525 g of a mixed solution of acrylic acid was dropped over 3 hours. After confirming that the acid value was 2.0 mg KOH / g or less and the oxirane oxygen concentration was 0.1% or less, the heating was stopped to obtain a solution containing an acrylic copolymer resin (P-1). In addition, "the total number of moles (total amount) of carboxyl groups in (meth) acrylic acid and (meth) acrylic acid ester having a carboxyl group relative to the total number of moles of epoxy groups in the acrylic copolymer resin" in the present synthesis example Is one. Property values of the solution containing the above-mentioned acrylic copolymer resin (P-1) are described below.
Viscosity: 1877 mPa · s / 25 ° C. Content of resin component: 50% by weight, hydroxyl value of resin component: 144 mg KOH / g, double bond equivalent: 270 g / mol

(Composition example 2)
In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, 1,800 g of butyl acetate was charged, and the internal temperature was set to 110 ° C. Add a solution of 742 g of glycidyl methacrylate, 47 g of methacrylic acid, 1210 g of methyl methacrylate, and 43 g of (2-ethylhexanoyl) (tert-butyl) peroxide as a polymerization initiator at room temperature for 5 hours. Dripped. Next, it was aged for 5 hours, and 8 g of (2-ethylhexanoyl) (tert-butyl) peroxide was added twice every 1 hour. Furthermore, in order to eliminate the polymerization initiator, the internal temperature was raised to 120 ° C. and then heated for 3 hours. Thereafter, the temperature was lowered to 105 ° C., and 7 g of 4-methoxyphenol as a stabilizer and 6 g of benzyldimethylamine as a reaction catalyst were added. Thereafter, 376 g of acrylic acid was dropped over 2 hours. It was confirmed that the acid value was 2.0 mg KOH / g or less and the oxirane oxygen concentration was 0.1% or less, and the temperature was lowered to 80 ° C. Next, 2 g of hydroquinone was added as a stabilizer, heating was stopped, and a solution containing an acrylic copolymer resin (P-2) was obtained. In addition, "the total number of moles (total amount) of carboxyl groups in (meth) acrylic acid and (meth) acrylic acid ester having a carboxyl group relative to the total number of moles of epoxy groups in the acrylic copolymer resin" in the present synthesis example Is one. Property values of the solution containing the above-mentioned acrylic copolymer resin (P-2) are described below.
Viscosity: 10519 mPa · s / 25 ° C., resin content: 54% by weight, resin component hydroxyl value: 120 mg KOH / g, double bond equivalent 450 g / mol

(Composition example 3)
In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, 1,800 g of butyl acetate was charged, and the internal temperature was set to 110 ° C. There, a solution prepared by mixing 622 g of glycidyl methacrylate, 47 g of methacrylic acid, 1330 g of methyl methacrylate, and 43 g of (2-ethylhexanoyl) (tert-butyl) peroxide as a polymerization initiator at normal temperature for 5 hours It dripped. Thereafter, it was aged for 5 hours, and 8 g of (2-ethylhexanoyl) (tert-butyl) peroxide was injected twice every one hour. Furthermore, in order to eliminate the polymerization initiator, the temperature was raised to 120 ° C., and heating was performed for 3 hours. The temperature was lowered to 105 ° C., 7 g of 4-methoxyphenol as a stabilizer and 4 g of benzyldimethylamine as a reaction catalyst were added. Thereafter, 315 g of acrylic acid was dropped over 2 hours. It was confirmed that the acid value was 2.0 mg KOH / g or less and the oxirane oxygen concentration was 0.1% or less, and the temperature was lowered to 80 ° C. 2 g of hydroquinone was added as a stabilizer, heating was stopped, and a solution containing an acrylic copolymer resin (P-3) was obtained. In addition, "the total number of moles (total amount) of carboxyl groups in (meth) acrylic acid and (meth) acrylic acid ester having a carboxyl group relative to the total number of moles of epoxy groups in the acrylic copolymer resin" in the present synthesis example Is one. Property values of the solution containing the above-mentioned acrylic copolymer resin (P-3) are described below.
Viscosity: 12462 mPa · s / 25 ° C Content of resin component: 53% by weight, hydroxyl value of resin component: 115 mg KOH / g, double bond equivalent 530 g / mol

(Composition example 4)
2,300 g of Santosol DME-1 dimethyl ester (Surface Specialties Japan Co., Ltd.) is introduced into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen substitution device, and a stirring device, and the internal temperature is maintained. Was set to 110.degree. A solution prepared by previously mixing 860 g of glycidyl methacrylate, 41 g of methacrylic acid, 662 g of methyl methacrylate, and 28 g of VAZO 67 as a polymerization initiator at normal temperature was dropped over 5 hours. Thereafter, the mixture was aged for 2 hours, and 6 g of VAZO 67 was further added 3 times every 1 hour. Furthermore, in order to eliminate the polymerization initiator, the temperature was raised to 125 ° C., and heating was performed for 5 hours. The temperature was lowered to 105 ° C., and 7 g of 4-methoxyphenol as a stabilizer and 7 g of benzyldimethylamine as a reaction catalyst were added. Thereafter, 436 g of acrylic acid was dropped over 1 hour. It was confirmed that the acid value was 2.0 mg KOH / g or less and the oxirane oxygen concentration was 0.1% or less, and the temperature was lowered to 80 ° C. In order to lower the viscosity, 260 g of Santosol DME-1 dimethyl ester was added and heating was stopped to obtain a solution containing an acrylic copolymer resin (P-4). In addition, "the total number of moles (total amount) of carboxyl groups in (meth) acrylic acid and (meth) acrylic acid ester having a carboxyl group relative to the total number of moles of epoxy groups in the acrylic copolymer resin" in the present synthesis example Is one. Property values of the solution containing the above-mentioned acrylic copolymer resin (P-4) are described below.
Viscosity: 5609 mPa · s / 25 ° C. Content of resin: 47% by weight, hydroxyl value of resin: 166 mg KOH / g, double bond equivalent 330 g / mol

(Composition example 5)
100 g of a solution containing the acrylic copolymer resin (P-1) obtained in Synthesis Example 1 was charged into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, and the internal temperature was Was set to 70.degree. Thereto 0.02 g (300 ppm relative to the resin content) of ankamine K54 was added as a reaction catalyst. After confirming that the solution was homogenized, the internal temperature was set to 80 ° C., and 19 g of RIKASHID MH-700F was added dropwise over 30 minutes. Then, it stirred at 80 degreeC for 15 hours, and obtained the solution containing the acryl-type copolymer resin (A-1) which has a (meth) acryloyl group and a carboxyl group in a side chain. Property values of the solution containing the acrylic copolymer resin (A-1) are described below.
Viscosity: 34,500 mPa · s / 25 ° C. Resin content: 62.6% by weight Resin acid value: 61 mg KOH / g Weight average molecular weight (resin content): 30,000
In addition, content of the monomer unit which has both a (meth) acryloyl group and a carboxyl group in the side chain with respect to the whole quantity of a monomer unit in acrylic type copolymer resin (A-1) was 50.8 weight%.

Synthesis Example 6
70 g of a solution containing the acrylic copolymer resin (P-1) obtained in Synthesis Example 1 was charged into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, and the internal temperature was Was set to 80.degree. Thereto, 0.5 g of RIKACID TMEG-200 was added. Thereafter, 0.02 g (400 ppm relative to the resin content) of benzyldimethylamine was added as a reaction catalyst and allowed to react for 3 hours. After confirming that the acid value did not change, 4 g of trimellitic anhydride was added. The reaction was carried out for 10 hours, and it was taken out after confirming that the acid value did not change. Thus, a solution containing an acrylic copolymer resin (A-2) having a (meth) acryloyl group and a carboxyl group in a side chain was obtained. Property values of the solution containing the acrylic copolymer resin (A-2) will be described below.
Viscosity: 15,600 mPa · s / 25 ° C., resin content: 54.2% by weight, resin acid value: 66 mg KOH / g, weight average molecular weight (resin content): 40,000
In addition, content of the monomer unit which has both a (meth) acryloyl group and a carboxyl group in the side chain with respect to the whole quantity of a monomer unit in acrylic type copolymer resin (A-2) was 19.4 weight%.

Synthesis Example 7
In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, 1,500 g of a solution containing the acrylic copolymer resin (P-2) obtained in Synthesis Example 2 is charged. The temperature was set to 70 ° C. 50 g of butyl acetate was charged. Subsequently, the internal temperature was set to 80 ° C., and 180 g of RIKACID MH-700F was dropped over 1 hour. Then, the reaction was carried out for 3 hours, and it was taken out after confirming that the acid value did not change. Thus, a solution containing an acrylic copolymer resin (A-3) having a (meth) acryloyl group and a carboxyl group in a side chain was obtained. Property values of the solution containing the acrylic copolymer resin (A-3) will be described below.
Viscosity: 55,000 mPa · s / 25 ° C. Resin content: 66.9% by weight Resin acid value: 61 mg KOH / g Weight average molecular weight (resin content): 30,000
In addition, content of the monomer unit which has both a (meth) acryloyl group and a carboxyl group in the side chain with respect to the whole quantity of a monomer unit in acrylic type copolymer resin (A-3) was 33.6 weight%.

Synthesis Example 8
100 g of a solution containing the acrylic copolymer resin (P-3) obtained in Synthesis Example 3 is charged into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, and the internal temperature is adjusted to It was set to 80 ° C. Thereto, 13 g of trimellitic anhydride was charged. Then, the reaction was carried out for 3 hours, and it was taken out after confirming that the acid value did not change. Thus, an acrylic copolymer resin (A-4) having a (meth) acryloyl group and a carboxyl group in a side chain was obtained. Property values of the solution containing the acrylic copolymer resin (A-4) are described below.
Viscosity: 48,000 mPa · s / 25 ° C., resin content: 65% by weight, resin acid value: 59 mg KOH / g, weight average molecular weight (resin content): 25,000
In addition, content of the monomer unit which has both a (meth) acryloyl group and a carboxyl group in the side chain with respect to the whole quantity of a monomer unit in acrylic type copolymer resin (A-4) was 34.2 weight%.

Synthesis Example 9
100 g of a solution containing the acrylic copolymer resin (P-4) obtained in Synthesis Example 4 was charged into a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement device, and a stirring device, and the internal temperature was It was set to 80 ° C. Thereto, 12 g of RIKACID MH-700F was dropped over 30 minutes. Then, the reaction was carried out for 3 hours, and it was taken out after confirming that the acid value did not change. Thus, a solution containing an acrylic copolymer resin (A-5) having a (meth) acryloyl group and a carboxyl group in a side chain was obtained. Property values of the solution containing the acrylic copolymer resin (A-5) will be described below.
Viscosity: 80,700 mPa · s / 25 ° C., resin content: 58.3% by weight, resin acid value: 65 mg KOH / g, weight average molecular weight (resin content): 30,000
In addition, content of the monomer unit which has a (meth) acryloyl group and a carboxyl group in the side chain with respect to the whole quantity of a monomer unit in acrylic type copolymer resin (A-5) was 37.5 weight%.

The details of the components used in the synthesis example of the acrylic copolymer resin (A) will be described below.
RIKACID MH-700F: 4-Methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture, manufactured by Shin Nippon Chemical Co., Ltd., neutralization value 686 mg KOH / g
RIKACID TMEG-200: ethylene glycol bisanhydrotrimellitate, Shin Nippon Rika Co., Ltd., acid anhydride equivalent 206
Trimellitic anhydride: Trimellitic anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd., 98.1% by weight of acid anhydride (purity)
Ankamine K54: Tris-2,4,6-dimethylaminomethyl-phenol, manufactured by Air Products & Chemicals, Inc. Santosol DME-1 Dimethyl ester: A mixture of dimethyl glutarate, dimethyl succinate and dimethyl adipate, surface • Specialties Japan KK EDGAC: Diethylene glycol monomethyl ether acetate, manufactured by Daicel Corporation

The weight average molecular weights of the acrylic copolymer resins (A-1) to (A-5) were determined by GPC (gel permeation gas chromatography) method based on standard polystyrene under the following measurement conditions. .
Equipment used: TOSO HLC-8220GPC
Pump: DP-8020
Detector: RI-8020
Column type: Super HZM-M, Super HZ4000, Super HZ3000, Super HZ2000
Solvent: Tetrahydrofuran Phase flow rate: 1 mL / min Column pressure: 5.0 MPa
Column temperature: 40 ° C
Sample injection volume: 10 μL
Sample concentration: 0.2 mg / mL

[Description of acrylic copolymer resin (B)]
The acrylic copolymer resin (B) will be described below.

Cyclomer PACA 230 AA: average molecular weight 14,000, resin acid value 40 mg KOH / g, made by Daicel Ornex Co. Cyclomer PACA 200 M: average molecular weight 12,000, resin acid value 110 mg KOH / g, made by Daicel Ornex Co. Cyclomer P ACAZ 250: average molecular weight 10,000, resin acid value 77 mg KOH / g, Daicel Ornex Co., Ltd.

[Description of Photopolymerization Initiator (C)]
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Japan Ltd.

[Description of evaluation method]
The evaluation method of heat stability and the evaluation method of hardenability are shown below.

(Evaluation of heating stability)
The 80 g of the composition prepared in the example was filled into a 100 ml heat bottle, the lid was closed, and the container was sealed so as not to leak. Thereafter, the heat-resistant bottle was put into a water bath at 80 ° C., and after 10 days, the appearance was observed and GPC measurement was performed.

  It is judged that the heating stability is bad when gel substances etc. are visually observed, or when the weight average molecular weight of the peak corresponding to the solid part (resin part) is 1.5 times or more compared to before the test by GPC analysis Then, it described as "x" in Tables 1-3. On the other hand, there is no gelation, and the weight average molecular weight is also less than 1.5 times as compared with the numerical value before the test. Described.

(Evaluation of curability)
One hundred parts of the composition prepared in the examples were coated on a glass plate using a bar coater, and heated at 80 ° C. for 10 minutes to remove the solvent. Then, it irradiated with ultraviolet rays on conditions of ² kW, 4 m / min, 1 Pass, and ultraviolet irradiation amount: about 400 mJ / cm ² .

  It is considered as poor curing if any appearance change such as whitening, swelling, or scratching is observed by manually rubbing a Kimwipe (made of paper waste, Nippon Paper Industries Cresia) impregnated with MEK against the coating film prepared. It described as "x" to -3. When no change in appearance was observed, it was judged that curing was sufficiently advanced, and described in Tables 1 to 3 as "○".

<Test result>
Said evaluation was performed about the active energy ray curable composition for photoresists by the composition described to Tables 1-3, and the evaluation result was described. In addition, acrylic copolymer resin (A) and acrylic copolymer resin (B) described the compounding quantity as a resin part. In addition, the active energy ray curable composition for photoresist is simply referred to as "curable composition". In the evaluation of heat stability, the curable compositions of Comparative Examples 2 and 4 caused gelation.

  As shown in the examples, the curable composition containing both the acrylic copolymer resin (A) and the acrylic copolymer resin (B) has good heat stability and good curability. It became clear. On the other hand, it becomes clear that the heat stability is significantly deteriorated when the acrylic copolymer resin (A) or the acrylic copolymer resin (B) is used alone as shown in the comparative example. The That is, in the above-mentioned evaluation of heat stability, in the case of a curable composition containing only the acrylic copolymer resin (A) or the acrylic copolymer resin (B), the resin reacts while the acrylic copolymer is reacted. It became clear that the curable composition which mixes and contains resin (A) and acrylic type copolymer resin (B) can suppress the reaction between the said resin.

Claims (8)

It is an active energy ray curable composition for a photoresist, which contains an acrylic copolymer resin (A), an acrylic copolymer resin (B), and a photopolymerization initiator (C),
The acrylic copolymer resin (A) is a monomer unit (UA1) having both a (meth) acryloyl group and a carboxyl group in the side chain, and a monomer unit (UA3) having a carboxyl group in the side chain (wherein, (UA1)) Acrylic copolymer resin containing
Acrylic copolymer resin (B) has a (meth) acryloyl group and a carboxyl group in a side chain, and the (meth) acryloyl group is derived from 3,4-epoxycyclohexylmethyl (meth) acrylate (meth) An active energy ray curable composition for a photoresist , which is an acryloyl group and is an acrylic copolymer resin having a resin skeleton different from that of the above-mentioned acrylic copolymer resin (A). The content of a monomer unit (UA1) having both a (meth) acryloyl group and a carboxyl group in a side chain is 15 to 70% by weight based on the total amount of monomer units constituting the acrylic copolymer resin (A). The active energy ray curable composition for photoresists of 1 . The acrylic copolymer resin (B) has a (meth) acryloyl group in the side chain and has no carboxyl group, and has a carboxyl group in the side chain and no (meth) acryloyl group. The active energy ray curable composition for photoresist according to claim 1 or 2 , which is an acrylic copolymer resin containing a monomer unit. The photoresist according to any one of claims 1 to 3 , wherein the acrylic copolymer resin (A) is an acrylic copolymer resin having at least a carboxyl group derived from polybasic acid anhydride in a side chain. Active energy ray curable composition. The resin acid value of the acrylic copolymer resin (A) is 30 to 200 mg KOH / g, and the weight average molecular weight is 5000 to 100000. The active energy ray curable composition for photoresist according to any one of claims 1 to 4. object. The active energy ray curable composition for photoresist according to any one of claims 1 to 5 , wherein the resin acid value of the acrylic copolymer resin (B) is 20 to 200 mg KOH / g, and the weight average molecular weight is 5,000 to 30,000. object. The active energy ray-curable composition for photoresists according to any one of claims 1 to 6 , wherein a resin acid value (X) obtained by the following formula is 40 to 105 mg KOH / g.
Resin acid number (X) (mg KOH / g) = (resin acid number of acrylic copolymer resin (A)) × a + (resin acid number of acrylic copolymer resin (B)) × b
a = content of acrylic copolymer resin (A) (g) / sum of content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g)
b = total content of acrylic copolymer resin (B) (g) / total content of acrylic copolymer resin (A) and acrylic copolymer resin (B) (g) A cured product of the active energy ray-curable composition for photoresist according to any one of claims 1 to 7 .