JP4529641B2 - Energy sensitive acid generator, acid generating method, and energy sensitive curable composition - Google Patents

Description

  The present invention relates to an energy-sensitive ray acid generator, a method for generating an acid from the acid generator, and further to an energy-sensitive ray curable composition and a method for producing a cured product using them. More specifically, an acid is generated by irradiation with energy rays, particularly light, and a cured product having good physical properties is obtained by reliably polymerizing a curable compound in a short time by a polymerization reaction or a crosslinking reaction using the generated acid as a catalyst. Regarding materials and methods that can be obtained, further, molding resins, casting resins, stereolithography resins, sealants, dental polymerization materials, printing inks, paints, photosensitive resins for printing plates, printing color proofs Resist for color filter, resist for black matrix, resist for printed circuit board, resist for semiconductor manufacturing, resist for microelectronics, resist for micromachine parts manufacturing, insulating material, hologram material, waveguide material, overcoat agent, adhesive Energy to obtain cured products with good physical properties in fields such as adhesives, adhesives, and release coatings Acid generator, a method for producing a cured product using the sensitive energy ray-curable composition and the curable composition. Furthermore, the present invention relates to other uses in which an acid is generated by irradiation with energy rays, particularly light, and the generated acid is used as a catalyst. Specifically, the coloring reaction of a dye precursor using the generated acid as a catalyst. For materials and methods for image formation, anti-counterfeiting, and energy dose detection using photon, and for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine parts using decomposition reaction catalyzed by generated acid The present invention relates to a material for a positive resist for manufacturing and the like.

  Because of their high reactivity, onium salts are known to be easily decomposed by irradiation with energy rays typified by light to generate various active species. Polymerization initiated by these active species Various uses such as a curing material and a resist material using a decomposition reaction have been proposed (Non-Patent Document 1).

A salt having a benzylsulfonium cation represented by the cation represented by the following general formula (3) is one of typical onium salts having both stability and reactivity, and is suitable for irradiation with heat or energy rays. It is known to function as an acid generator or a radical generator in response.

  For example, as the heat latent polymerization catalyst, the sulfonium salt hexafluoroantimonate and the like are disclosed (Patent Document 1, Patent Document 2, etc.).

  Examples that function as an acid generator by light include benzylsulfonium salts having an alkoxybenzyl group (Patent Documents 3 and 4). Further, an acid generator using a boron-based anion typified by tetrakis (pentafluorophenyl) borate is also disclosed in order to improve the solubility and sensitivity when the sulfonium salt is used as an acid generator ( Patent Document 5).

  Furthermore, in recent years, benzylsulfonium salts function as acid generators in response to short-wavelength excimer lasers, etc., as acid generators for resists for ultra-fine processing, which have been proposed to support high integration of semiconductors. Is disclosed (Patent Document 6, etc.).

  In general, the cation portion of the onium salt is often a factor that determines the amount of acid generated from the acid generator upon irradiation with energy rays, that is, the sensitivity of the energy-sensitive acid generator. Specifically, it is considered that the efficiency of acid generation is determined as a comprehensive factor such as absorption characteristics, oxidation-reduction potential, chemical bond strength and orientation of the cation moiety in the energy-sensitive acid generator.

  Energy rays used to generate an acid by irradiating an energy-sensitive acid generator are diverse, such as X-rays, ultraviolet rays, visible rays, infrared rays, and electron beams. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps and the like belong to the most general light sources, and when these light sources are used, light having a main wavelength in the wavelength region of 300 nm to 450 nm is irradiated. (Non-Patent Document 1) In order to deal with these light sources, studies have been conducted to improve the sensitivity of the acid generator with respect to irradiation with energy rays in the above wavelength region.

In general, an acid generator having a benzylsulfonium cation represented by the general formula (3) cannot be expected to have good sensitivity when irradiated with light in a wavelength region of 300 nm to 450 nm, and particularly absorbs completely on the long wavelength side of the above wavelength region. Therefore, it cannot function with a general light source as an acid generator. In order to improve this point, the benzene ring portion of the cation structure represented by the general formula (3) is replaced with an aromatic ring having absorption in the above-mentioned wavelength region, that is, a chromophore such as a naphthalene ring or an anthracene ring, thereby absorbing light. Has been proposed (Patent Document 5). As another method, a method of using a material having an absorption suitable for the above wavelength and capable of functioning as a sensitizer of a benzylsulfonium salt has been proposed. For example, an anthracene is used as a sensitizer. There is known a method of using a kind (Patent Document 8). In addition, although it is a radical polymerization initiator from which an application and an action mechanism differ completely, the example using a coumarin skeleton as such chromophore is disclosed (patent document 7).
JP 58-37003 A Japanese Unexamined Patent Publication No. 63-222002 Japanese Patent Laid-Open No. 3-17101 JP-A-2-196812 JP 9-176112 A JP-A-8-314130 Japanese Patent Laid-Open No. 2001-213909 Japanese Patent Laid-Open No. 11-322952 Radtech Study Group “Current Status and Prospects of UV / EB Curing Technology” CM Publishing (2002)

  Although the properties of benzylsulfonium salts as energy-sensitive linear acid generators have been improved through the above-described studies, the acid generator alone is sufficient in terms of acid generation sensitivity to light irradiation in the wavelength region of 300 nm to 450 nm. This is a situation in which no material having the above has been found.

As mentioned earlier, the amount of acid generated by irradiation with energy rays, that is, the sensitivity of acid generation depends on the cation site, and in other words, no particularly effective benzylsulfonium salt-based cation has been found in this wavelength region. Can do. For example, as described above, the benzylsulfonium cation represented by the general formula (3) does not have effective sensitivity to light irradiation in the above wavelength region. A benzylsulfonium salt-based material having a substituent has also been proposed, but there are hardly any materials having good absorption characteristics and sensitivity in the above wavelength region. In addition, in order to improve the absorption characteristics, it has been proposed to replace the benzene ring of the cation represented by the general formula (3) with a naphthalene ring or an anthracene ring (Patent Document 5), but the improvement of the absorption characteristics is not necessarily performed. It does not necessarily lead to an increase in sensitivity, and there are very few guidelines for specific molecular design. In fact, benzylsulfonium salts having a naphthalene ring do not have sufficient sensitivity in the above-mentioned wavelength region, and there is a need for further improvement in sensitivity to energy rays in order to improve productivity. Is not enough material.
Further, as a radical polymerization initiator, a sulfonium salt in which the benzene ring of the general formula (3) is replaced with a coumarin structure is disclosed (Patent Document 7), but it is used only with a radical polymerizable compound. It is unknown whether the decomposition mechanism and the mechanism of action function as completely different acid generators.

  In addition, a method for expressing sensitivity in a wavelength region of 300 nm to 450 nm by using a combination of benzylsulfonium salts and a sensitizer has been proposed. This method is an effective method for phenacylsulfonium salts. Since electron transfer from the sensitizer is not likely to occur, it is difficult to express sufficient sensitivity. In addition, sensitizers having suitable absorption in these wavelength regions are often colored, and depending on the application, the addition amount is limited, and sufficient sensitivity cannot often be exhibited. In fact, sensitization with anthracene has been shown to improve the sensitivity of benzylsulfonium salts during light irradiation in the wavelength region of 300 nm to 450 nm. However, the sensitivity to energy-sensitive rays has been further improved to improve productivity. The current situation is not enough.

（式中、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、およびＲ₀₆はそれぞれ独立に、水素原子、アル
キル基、アリール基、アルケニル基、アシル基、アルコキシル基、アリールオキシ基、ア
シルオキシ基、アルコキシカルボニルオキシ基、アミノ基またはハロゲン原子を表す。
ただし、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、およびＲ₀₆のうち少なくとも一つは、

を表す。Ｒ₁₁およびＲ₁₂は、それぞれ独立に、水素原子、アルキル基、アリール基、アル
コキシル基またはアルケニル基を表す。
Ｒ₂₁およびＲ₂₂は、それぞれ独立に、アルキル基、アリール基またはアルケニル基を表す
。
ただし、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、Ｒ₀₆、Ｒ₁₁、Ｒ₁₂、Ｒ₂₁、およびＲ₂₂は、一体
となって、環を形成してもよい。
Ｘ^-は、下記一般式（２）で表記されるボレートである上記感エネルギー線酸発生剤に関
する。
一般式（２）

（ただし、Ｙはフッ素または塩素原子、
Ｚは、フッ素原子、シアノ基、ニトロ基、およびトリフルオロメチル基の中から選ばれる
基で２つ以上置換されたフェニル基、
ｍは０から３の整数、ｎは１から４の整数を表し、ｍ＋ｎ＝４である。）
As a result of intensive studies to solve the above problems in consideration, the present inventors have found that the efficiency of acid generation with respect to energy rays, particularly light irradiation in the wavelength region of 300 nm to 450 nm without using a sensitizer, that is, As a result, a material whose sensitivity has been innovatively improved as compared with conventionally known benzylsulfonium salts has been found. That is, the present invention relates to an energy-sensitive linear acid generator represented by the following general formula (1).
General formula (1)

(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group) Represents a group, an alkoxycarbonyloxy group, an amino group or a halogen atom.
Provided that at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ is

Represents. R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ may be combined to form a ring.
X ⁻ relates to the energy-sensitive linear acid generator which is a borate represented by the following general formula (2).
To do.
General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group
A phenyl group substituted by two or more groups,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. )

である上記記載の感エネルギー線酸発生剤。 Further, the present invention provides that R ₀₂ is

The energy-sensitive linear acid generator as described above.

  Furthermore, the present invention relates to an acid generation method in which the energy sensitive acid generator is irradiated with light in a wavelength region of 300 nm to 450 nm to generate an acid.

  Furthermore, this invention relates to the energy sensitive ray curable composition containing the said energy sensitive ray acid generator (A) and an acid curable compound (B).

  Furthermore, this invention relates to the manufacturing method of hardened | cured material which irradiates and hardens the energy ray containing the light of the wavelength range of 300 nm to 450 nm to the said energy sensitive ray curable composition.

  The energy-sensitive linear acid generator of the present invention replaces the benzene ring portion of the benzylsulfonium cation with a specific substituent, that is, a coumarin skeleton which may have a substituent, thereby producing an energy ray, particularly 300 nm to 450 nm. It has good absorption characteristics in the wavelength region, and can function as a highly sensitive photoacid generator for light irradiation in the wavelength region without using a sensitizer. Yes. Therefore, when the energy-sensitive linear acid generator of the present invention is used, a polymerization reaction, a crosslinking reaction, a decomposition reaction, a coloring reaction, etc., using an acid generated from a conventionally known benzylsulfonium salt-based energy-sensitive linear acid generator as a catalyst. Can be reliably realized in a shorter time, and as a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions.

  Hereinafter, embodiments of the present invention will be described in detail.

First, the energy sensitive acid generator of the present invention will be described. The energy-sensitive linear acid generator of the present invention is characterized by having a specific structure at the cation site, so that energy rays, particularly 300
A significant increase in sensitivity to light irradiation in the wavelength region from nm to 450 nm is realized. For this reason, the energy-sensitive linear acid generator of the present invention achieves significantly higher sensitivity and improved characteristics as compared with conventionally known benzylsulfonium salt-based energy-sensitive linear acid generators if the anion species are the same. it is possible.

  The energy-sensitive linear acid generator of the present invention has a structure represented by the general formula (1), and the benzene ring portion of the benzylsulfonium cation is replaced with a coumarin skeleton which may have a substituent. Has a characteristic structure. By introducing this substituent, light absorption characteristics suitable for a wavelength region of 300 nm to 450 nm can be imparted to the sulfonium cation. In addition, by having this structure, the sulfonium cation of the present invention decomposes very efficiently without using a sensitizer in combination with light irradiation in the wavelength region. It is possible to function as a highly sensitive material that is generated automatically.

（式中、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、およびＲ₀₆はそれぞれ独立に、水素原子、アル
キル基、アリール基、アルケニル基、アシル基、アルコキシル基、アリールオキシ基、ア
シルオキシ基、アルコキシカルボニルオキシ基、アミノ基またはハロゲン原子を表す。
ただし、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、およびＲ₀₆のうち少なくとも一つは、

を表す。Ｒ₁₁およびＲ₁₂は、それぞれ独立に、水素原子、アルキル基、アリール基、アル
コキシル基またはアルケニル基を表す。
Ｒ₂₁およびＲ₂₂は、それぞれ独立に、アルキル基、アリール基またはアルケニル基を表す
。
ただし、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃、Ｒ₀₄、Ｒ₀₅、Ｒ₀₆、Ｒ₁₁、Ｒ₁₂、Ｒ₂₁、およびＲ₂₂は、一体
となって、環を形成してもよい。
Ｘ^-は、下記一般式（２）で表記されるボレートである。）
一般式（２）

（ただし、Ｙはフッ素または塩素原子、
Ｚは、フッ素原子、シアノ基、ニトロ基、およびトリフルオロメチル基の中から選ばれる
基で２つ以上置換されたフェニル基、
ｍは０から３の整数、ｎは１から４の整数を表し、ｍ＋ｎ＝４である。）
General formula (1)

(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group) Represents a group, an alkoxycarbonyloxy group, an amino group or a halogen atom.
Provided that at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ is

Represents. R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ may be combined to form a ring.
X ⁻ is a borate represented by the following general formula (2) . )
General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group
A phenyl group substituted by two or more groups,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. )

  One specific example of the energy-sensitive linear acid generator of the present invention is shown as compound (1).

Compound (1)

  The absorption spectrum of compound (1) in acetonitrile is shown in FIG. In addition, the absorption spectrum of the conventional benzylsulfonium compound (2) as a comparative compound is also shown in FIG.

Compound (2)

  As can be seen from FIG. (1), compound (2) does not have a suitable absorption in the wavelength region of 300 nm or more, but compound (1) has an absorption maximum with a molar extinction coefficient of 12800 at 332 nm. It has suitable absorption in the wavelength region of 450 nm.

  Further, the compound (1) which is an energy-sensitive line acid generator of the present invention is a transparent material having a molar extinction coefficient of 2100 at 365 nm corresponding to one of the emission lines of a mercury lamp, for example. When irradiated with light, the acid generation significantly exceeds the sensitivity when compound (2), which is a conventionally known benzylsulfonium acid generator having the same anion, is used alone or in combination with a sensitizer. It is a material that has an innovative function as an agent.

At present, details of the reaction mechanism of acid generation by light irradiation are not clear, but the sulfonium cation part of compound (1) decomposes by absorbing energy rays to generate protons, and anion X ⁻ is counter anion. It is considered that the acid, ie, H ⁺ X ⁻ is generated. At that time, it is considered that by having a specific cation structure, suitable energy ray absorption characteristics are imparted, and at the same time, decomposition proceeds efficiently due to a substituent effect in an excited state.

  The energy ray source used for generating the acid from the energy-sensitive ray acid generator of the present invention is not particularly limited, but a light source capable of irradiating light in a wavelength region of 300 nm to 450 nm that expresses particularly suitable sensitivity is preferable, and Other energy rays may be emitted simultaneously with the light in the wavelength region. A particularly preferable light source is a light source having a main wavelength of light emission in a wavelength region of 300 nm to 450 nm. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, and a xenon. Examples include, but are not limited to, lamps and pulsed light xenon lamps. Also suitable are lasers having an emission wavelength in the wavelength region of 300 nm to 450 nm, such as Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, and semiconductor excitation solid laser. It can be used as an energy ray source. An electron beam can also be used as a suitable energy beam source. All of the energy-sensitive acid generators (A) of the present invention have suitable absorption in the wavelength region of 300 nm to 450 nm and the absorption characteristics are slightly different depending on the substituent, but by appropriately selecting the light source described above, It can function as a highly sensitive energy-sensitive linear acid generator. In addition, these light sources can be appropriately irradiated through optical devices such as filters, mirrors, and lenses.

  Next, the structure of the energy-sensitive linear acid generator of the present invention will be described in detail.

  The general formula (1) and the general formula (2) can introduce various substituents as long as the energy-sensitive linear acid generator of the present invention does not inhibit the properties thereof. By introducing a substituent, the energy-sensitive linear acid generator of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in the resin or solvent used together.

The substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ in the general formula (1) are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an acyl group, an alkoxyl group, An aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an amino group or a halogen atom is represented.

As the alkyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1), a straight chain, branched chain, monocyclic group having 1 to 18 carbon atoms or Examples include condensed polycyclic alkyl groups, and specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, Isopropyl group, isobutyl group, isopentyl group, sec-butyl group, t-butyl group, sec-pentyl group, t-pentyl group, t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Examples include adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, and the like. It is not specified.

The aryl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) is a monocyclic or condensed polycyclic group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples thereof include a phenyl aryl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-indenyl group, a 9-fluorenyl group, a 2-furyl group, and 2 -Thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group and the like can be mentioned, but are not limited thereto. .

_Examples of the alkenyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) include linear, branched, monocyclic or C _1-18 Examples thereof include a condensed polycyclic alkenyl group, which may have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, and a 2-butenyl group. 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4- Examples include hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, and the like. However, it is not limited to these.

As the acyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1), a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms, Examples thereof include a carbonyl group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyl group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded. May have an unsaturated bond in the structure, specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, Palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoy Group, isocrotonoyl group, oleoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, etc. It is not limited to.

As the alkoxyl group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1), a straight chain, branched chain, monocyclic group having 1 to 18 carbon atoms or Specific examples include condensed polycyclic alkoxyl groups. Specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group. Group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group , Cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclo Examples include hexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, and the like. It is not something.

The aryloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) is a monocyclic or condensed having 4 to 18 carbon atoms which may contain a hetero atom Specific examples include polycyclic aryloxy groups, and specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, a 9-phenanthryloxy group, a 1-pyrenyloxy group, and 5-naphtha. Senyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group Group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto.

As the acyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1), a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms, Examples thereof include a carbonyloxy group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyloxy group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded. Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, Cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyl Ruoxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group , 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group and the like, but are not limited thereto.

Examples of the alkoxycarbonyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) include C _1-12 carbonic acid ester groups, and specific examples As t-butoxycarbonyloxy group, t-pentyloxycarbonyloxy group, 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group, 2-tetrahydropyranyloxycarbonyloxy group , 1-ethylcyclopentyloxycarbonyloxy group and the like can be mentioned, but are not limited thereto.

_Examples of the amino group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) include an amino group, a dialkylamino group, a diarylamino group, and an alkylarylamino group. Specific examples include amino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group, morpholino group, piperidino group, benzylmethylamino group, diphenylamino group, ditolylamino group, N- Although a carbazolyl group etc. are mentioned, it is not limited to these.

Examples of the halogen atom in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

The alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the above general formula (1) Group, alkoxycarbonyloxy group, amino group may be further substituted with other substituents, such as hydroxyl group, mercapto group, cyano group, nitro group, halogen atom, alkyl group. Groups, aryl groups, acyl groups, alkoxyl groups, aryloxy groups, acyloxy groups, alkylthio groups, arylthio groups, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, Examples include t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, 2-furanyl group, 2-thienyl group, 2-indolyl group , 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 18 monocyclic or condensed polycyclic aromatic carbonyl groups, which may have an unsaturated bond in the structure. Specific examples thereof include formyl group, acetyl group, propionyl group, Butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group Benzoyl group, 1-naphthoyl group, 2-naphthoyl group, N'namoiru group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, and the like 5 Nafutasenoiru group.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

  Examples of the aryloxy group include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, 9 -Anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluore Nyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples include a carbonyloxy group having 4 to 18 monocyclic or condensed polycyclic aromatics bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth A royloxy group, a 5-naphthacenoyloxy group, etc. can be mentioned.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3 -A carbazolylthio group, a 4-carbazolylthio group, etc. can be mentioned, However, It is not limited to these.

The substituents in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ in the general formula (1) do not have to be the same, and the above substituents are used in any combination. be able to. Particularly preferred substituents for the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R _05, and R ₀₆ include groups selected from a hydrogen atom, an alkyl group, an alkoxyl group, an aryloxy group, and an acyloxy group. More preferably, an alkoxyl group is mentioned, and most preferably, the substituent R ₀₅ is an alkoxyl group, and particularly good light absorption characteristics and sensitivity can be realized. Two adjacent substituents selected from R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R _05, and R ₀₆ may be combined to form a cyclic structure.

The alkyl group, aryl group, alkoxyl group and alkenyl group in the substituents R ₁₁ and R ₁₂ in the general formula (2), the alkyl group, aryl group and alkenyl group in R ₂₁ and R ₂₂ are the substituents R ₀₁ , R _The same substituents as those exemplified as the alkyl group, aryl group, alkoxyl group, and alkenyl group in ₀₂ , R ₀₃ , R ₀₄ , R _05, and R ₀₆ can be given.

The substituent R ₂₁ is bonded to any one of R ₂₂ , R ₁₁ , R ₁₂ , R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ via a divalent organic residue, and a ring structure May be formed. In addition, the substituent R ₁₁ may be bonded to any of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ via a divalent organic residue to form a ring structure. The divalent organic residue here is an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or -C = C-, —O—, —S—, —NH—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O—, and a combination thereof. An alkylene group which may have a substituent is meant.

であり、その置換位置は特に限定されないが、置換位置がＲ_０２の場合、合成難易度が比較的低く、良好な吸収特性と酸発生感度が実現できるため特に好ましい。 In the general formula (1), any one of the substituents R ₀₁ to R ₀₆ is

The substitution position is not particularly limited, but the substitution position of R ₀₂ is particularly preferred because the synthesis difficulty is relatively low and good absorption characteristics and acid generation sensitivity can be realized.

Next, the anion X ⁻ in the general formula (1) will be described.

The anion X ⁻ in the general formula (1) is a borate anion represented by the following general formula (2) . These are relatively easy to synthesize, generated acid is very strong, that have a high solubility and high safety and hygiene.

（ただし、Ｙはフッ素または塩素原子、
Ｚは、フッ素原子、シアノ基、ニトロ基、トリフルオロメチル基の中から選ばれる基で２つ以上置換されたフェニル基、
ｍは０から３の整数、ｎは１から４の整数を表し、ｍ＋ｎ＝４である。） General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is a phenyl group substituted with two or more groups selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. )

  As the substituent Z in the general formula (2), 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2 , 4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-trifluoro-3,5-bis (trifluoromethyl) phenyl group, 3,5 -Dinitrophenyl group, 2,4,6-trifluoro-3,5-dinitrophenyl group, 2,4-dicyanophenyl group, 4-cyano-3,5-dinitrophenyl group, 4-cyano-2,6- Examples thereof include, but are not limited to, bis (trifluoromethyl) phenyl group.

  Therefore, as the structure of the borate anion represented by the general formula (2), specifically, pentafluorophenyl trifluoroborate, 3,5-bis (trifluoromethyl) phenyl trifluoroborate, bis (pentafluorophenyl) ) Difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate, tetrakis (penta Fluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

  Among these, tetrakis (pentafluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate are particularly preferable as the anion represented by the general formula (2).

  The energy sensitive acid generator represented by the general formula (1) of the present invention comprises a combination of the sulfonium cation and various anions exemplified above.

Specific structures are shown below, but the structure of the energy-sensitive linear acid generator of the present invention is not limited thereto.

However, in the above structural formula X- may be any anion selected from the structures shown below.

The synthesis method for obtaining the energy-sensitive linear acid generator of the present invention is not particularly limited, and the structure can be easily synthesized and confirmed by appropriately combining conventionally known chemical reactions, post-treatment methods, purification methods and analysis methods. Is possible. As a synthesis method of benzylsulfonium salt,
It is described in a new experimental chemistry course (edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

As an example of the synthesis method, a coumarin derivative having a bromomethyl group is synthesized as a starting material. If necessary, this coumarin derivative can also be easily synthesized by combining conventionally known chemical reactions. By reacting this coumarin derivative having a bromomethyl group with a sulfide, the bromide salt of sulfonium having a coumarin structure of the present invention can be easily synthesized. In order to promote the sulfoniumation reaction, it is possible to heat as necessary, or to add a silver catalyst typified by silver hydroxide, silver nitrate, silver perchlorate and silver tetrafluoroborate. Thus obtained sulfonium salt having a coumarin structure can be easily ion-exchanged with a metal salt having an anion X ^−, and the energy-sensitive linear acid generator of the present invention can be obtained.

  The energy-sensitive linear acid generator of the present invention functions as a highly sensitive photoacid generator when irradiated with energy rays, particularly in the wavelength region of 300 nm to 450 nm. As a result, it is possible to realize polymerization reactions, crosslinking reactions, decomposition reactions, color development reactions, etc. using the acid as a catalyst in a shorter time. As a result, the sensitivity and characteristics of various applications using these reactions are greatly improved. It becomes possible to realize the improvement. Below, the utilization method of the energy-sensitive linear acid generator of this invention is described.

  The composition having various functions containing the energy-sensitive linear acid generator of the present invention described below is used in combination with a known acid proliferating agent as necessary in order to further improve the sensitivity to the energy rays. Can do. The acid proliferator is a material that generates further acid by a thermal decomposition reaction using the acid generated from the acid generator as a catalyst, and the acid generated from the acid proliferator itself can decompose other acid proliferators. Therefore, it becomes possible to dramatically improve the acid concentration by using the acid proliferating agent. Such an acid proliferating agent is not particularly limited, but specific examples include materials described in JP-A-8-248561, JP-A-10-1508, and JP-A-5-297576.

  The composition containing the energy-sensitive linear acid generator (A) and the acid-curable compound (B) of the present invention is cured quickly and reliably by irradiation with energy rays, particularly in the wavelength region of 300 nm to 450 nm. It can be used as an energy-sensitive ray-curable composition capable of obtaining a cured product having characteristics.

  The acid curable compound (B) used for the energy-sensitive ray curable composition of the present invention will be described. Here, the acid curable compound (B) is polymerized by the action of energy ray irradiation, particularly light irradiation in a wavelength region of 300 nm to 450 nm in the coexistence with the energy sensitive acid generator (A) of the present invention. Alternatively, it means a compound that can be converted into a high molecular weight substance by a crosslinking reaction, and includes the following compounds or mixtures thereof.

  First, an acid-curable compound (B) is a compound that becomes high molecular weight by crosslinking or polymerization reaction under the acid catalyst generated from the energy-sensitive linear acid generator (A) or in combination with heating. can give. A typical example is a compound having a structure represented by the following general formula (4) as a compound having a methylol group as a formaldehyde precursor or a substituted methylol group.

General formula (4)

(In the general formula (4), A is a group represented by G or G-H-G, and G is a substituted or unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group, or oxygen, sulfur, A nitrogen-containing heterocyclic group, H represents a single bond or an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or —O —, —S—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O— and a substituent having such a bond in part. A may be a polymer such as a phenol resin, and Q and Q ′ are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, An aryl group which may have a substituent, an arylalkyl group, Others .r which means an acyl group is an integer of 1 to 3, s is an integer of 0-3.)

  Here, as the substituted or unsubstituted mononuclear or condensed polynuclear aromatic hydrocarbon group represented by G to H in the general formula (4), an o-phenylene group, an m-phenylene group, a p-phenylene group, 4-methyl-1,2-phenylene group, 4-chloro-1,2-phenylene group, 4-hydroxy-1,2-phenylene group, 2-methyl-1,4-phenylene group, p, p'-biphenylylene Group, 1,2-naphthylene group, 9,10-anthrylene group, 2,7-phenanthrylene group, etc.

  Examples of the oxygen-, sulfur- and nitrogen-containing heterocyclic groups include 2,5-furylene group, 2,5-thienylene group, 2,4-oxazolylene group, 2,4-thiazolylene group, 2,5-benzofurylene group, 2, 5-benzothienylene group, 2,6-pyridylene group, 5,8-quinolylene group, etc.

  Examples of the alkylene group which may have a substituent having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylmethylene group, a chloromethylene group, a dimethylmethylene group, and a bis (trimethyl group). Fluoromethyl) methylene group, etc.

  Examples of the arylene group which may have a substituent include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4-methyl-1,2-phenylene group, a 4-chloro-1,2-phenylene group, 4-hydroxy-1,2-phenylene group, 2-methyl-1,4-phenylene group, p, p'-biphenylylene group, 1,2-naphthylene group, 9,10-anthrylene group, 2,7-phenanthrylene group As the arylalkylene group, benzylidene group, p-tolylmethylene group, 2-naphthylmethylene group, etc.

Or a substituent having a —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, or —SO ₂ —O— bond in part. Examples of the alkylene group that may be used include a methylenedioxy group, an ethylenedioxy group, a propylenedioxy group, a diethylenedioxy group, a triethylenedioxy group, a methylenedithio group, an ethylenedithio group, a propylenedithio group, and a diethylenedithio group. , triethylene dithio group, a methylenedioxy sulfonyl group, ethylenedioxy sulfonyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, _-OOC-CH 2 -COO- group, -OOC- _{(CH 2) 2} -COO- group , —CH ₂ —OCOO—CH ₂ — group, —CH ₂ — (OCOO—CH ₂ ) ₂ — group, and the like.

Examples of the alkyl group having 1 to 4 carbon atoms represented by Q and Q ′ in the general formula (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc.
As the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc.

As the aryl group which may have a substituent, a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, p- A cyanophenyl group, a p-nitrophenyl group, a 3,5-bis (trifluoromethyl) phenyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-dimethylaminophenyl group, a p-phenylthiophenyl group, etc. Examples of the arylalkyl group include a benzyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a phenethyl group, a styryl group, and a cinnamyl group.
Examples of the acyl group include an acetyl group, a hexanoyl group, a benzoyl group, a cyclohexanoyl group, a methoxalyl group, and a salicyloyl group.

  Specific examples of such acid curable compounds (B) include various aminoplasts or phenoplasts, that is, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins and monomers thereof. Or an oligomer. Many of these are commercially available for applications such as paint vehicles. For example, Cymel (registered trademark) 300, 301, 303, 350, 370, 380, 1116, 1130, 1123, 1125, 1170, etc. manufactured by American Cyanamid, Inc., or Nikarak (registered trademark) Mw30 manufactured by Sanwa Chemical Co., Ltd. A typical example is a series of Mw30M, Mw30HM, Mx45, Bx4000 and the like. These may be used alone or in combination of two or more.

  Another specific example of the acid curable compound (B) is a methylolated or alkoxydimethylated phenol derivative that can be a formaldehyde precursor. These may be used as a monomer, or may be used as a resin such as a resol resin or a benzyl ether resin.

  Furthermore, as another system of the acid curable compound (B), compounds having a silanol group, for example, compounds disclosed in JP-A-2-154266 and JP-A-2-173647 can be mentioned.

  Also, a mixture of polyene and polythiol, such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl carbonate, triallyl isocyanurate, urethane polyene produced from polyisocyanate and allyl alcohol (eg hexamethylene diisocyanate and allyl) A compound selected from, for example, a urethane compound obtained by a polycondensation reaction of alcohol, and a compound selected from, for example, trimethylolpropane trithiol glycolate, pentaerythritol-tetra-3-mercaptopropionate, etc. as polythiol Can also be illustrated as an acid-curable compound (B).

  Moreover, the alkoxysilanes shown below can also be mentioned as an acid-curable compound (B). Specific examples include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyl. Compounds having an alkoxysilyl group such as trimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, more specifically, Toray Dow Corning product catalog, page 59 or Shin-Etsu silicone silane "Silane coupling agent" described in the coupling agent product catalog (issued in September 1987), Toray Dow Corning product catalog, page 61 or Toshiba Silicone Corporation general catalog, page 27 (published in April 1986) Compounds having an alkoxysilyl group, known in the industry as "silane compound" described is, can be cited as alkoxysilanes.

  Furthermore, examples of the acid curable compound (B) include a compound capable of cationic polymerization or a mixture thereof. The compounds capable of cationic polymerization here include, for example, epoxy compounds, styrenes, vinyl compounds, vinyl ethers, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, cyclic ethers, lactones, and oxazolines. Aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams and aryldialdehydes. Further, polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in the chain are also included in the acid curable compound (B).

  First, examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and further epoxide monomers and episulfite monomers. Examples of aromatic epoxy compounds include monofunctional epoxy compounds such as phenyl glycidyl ether, polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof, such as bisphenol A, Bisphenol compounds such as tetrabromobisphenol A, bisphenol F, and bisphenol S, or glycidyl ethers produced by the reaction of adducts of alkylene oxides (eg, ethylene oxide, propylene oxide, butylene oxide) of bisphenol compounds with epichlorohydrin, novolak type Epoxy resins (for example, phenol novolac epoxy resin, cresol novolac epoxy resin, brominated phenol novolac epoxy resin) ), Trisphenolmethane triglycidyl ether.

  Examples of alicyclic epoxy compounds include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl). ) Adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHPE-3150 (Daicel Chemical Industries ( Co., Ltd. Alicyclic epoxy resin (softening point 71 ° C.), and the like.

  Examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl. Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, tri Methylolpropane monoglycidyl ether, trimethylolpropane triglycidyl Ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether.

  Examples of styrenes include styrene, α-methyl styrene, p-methyl styrene, p-chloromethyl styrene and the like. Examples of the vinyl compound include N-vinyl carbazole and N-vinyl pyrrolidone.

  Examples of vinyl ethers include n- (or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4 butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether. , Tetraethylene glycol divinyl ether, propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, tri Methylolpropa Trivinyl ether, diglycerol trivinyl ether, sorbitol tetravinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) Alkyl vinyl ethers such as trifluoropropane divinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, ethynyl vinyl ether, alkynyl vinyl ethers such as 1-methyl-2-propenyl vinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, p- Methoxyphenyl vinyl ether, bisphenol A divinyl ether, Aryl vinyl ethers such as labromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, 1,4-benzenedimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether, m-phenylene Examples thereof include aralkyl divinyl ethers such as bis (ethylene glycol) divinyl ether, urethane polyvinyl ether (for example, VECtomer 2010 manufactured by ALLIED-SIGNAL), and the like.

  Spiro orthoesters include 1,4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane, 1,4,6-trio. Xaspiro (4,5) decane and the like include bicycloorthoesters such as 1-phenyl-4-ethyl-2,6,7-trioxabicyclo (2,2,2) octane, 1-ethyl-4- Hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like are spiro orthocarbonates such as 1,5,7,11-tetraoxaspiro (5,5) undecane, 3 , 9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane and the like.

  Examples of cyclic ethers include oxetanes such as oxetane and phenyloxetane, tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydropyrans such as tetrahydropyran and 3-propyltetrahydropyran, trimethylene oxide, and s-trioxane. It is done. Examples of lactones include β-propiolactone, γ-butyllactone, δ-caprolactone, and δ-valerolactone. Examples of oxazolines include oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.

  Examples of aziridines include aziridines and N-ethylaziridines. Examples of cyclosiloxanes include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, and triphenyltrimethylcyclotrisiloxane. The ketals include 1,3-dioxolane, 1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-dioxolane. Etc.

  Examples of cyclic acid anhydrides include phthalic anhydride, maleic anhydride, and succinic anhydride, and examples of lactams include β-propiolactam, γ-butyrolactam, and δ-caprolactam. Examples of aryldialdehydes include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.

  Although there is no special limitation in each component mixture ratio in the above energy sensitive ray-curable compositions, an energy sensitive acid generator (A) is 0 with respect to 100 weight part of acid-curable compounds (B). It is preferably used in a ratio of 0.01 to 40 parts by weight, preferably 0.1 to 25 parts by weight.

  The energy-sensitive ray-curable composition of the present invention can be used as it is in the form of a liquid or fluid adhesive, adhesive, adhesive, sealant, paint, surface coating agent, stereolithography resin, light It can be used for dental resins and the like by adding fillers such as hydroxide apatite to proofing materials, printing inks, ink jet inks, etc. by adding dyes, pigments, etc. to forming sheets.

  As the pigment, both inorganic pigments and organic pigments can be used. Examples of inorganic pigments include carbon black and titanium oxide, and examples of organic pigments include azo, phthalocyanine, quinacridone, perylene, perinone, isoindolinone, quinophthalone, dioxazine, anthraquinone, indigo, Conventionally used ones such as methine and diketopyrrolopyrrole can be used. These pigments can be used in combination in order to optimize the hue. In addition, these pigments can be dispersed in the form of fine particles using an appropriate disperser in order to improve uniformity, stability over time and transparency. It is also possible to use a dispersant such as a pigment derivative in combination.

  Examples of the dye include oil-soluble dyes and basic dyes. Specifically, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (orientated chemistry) Kogyo Co., Ltd.), crystal violet (CI-42555), methyl violet (CI-42535), rhodamine B (CI-45170B), malachite green (CI-422000), methylene blue (CI-52015) and the like. However, it is not limited to these.

  In addition, various polymer polymers are used as binders, mixed and dissolved in a solvent, and applied to glass plates, aluminum plates, silicon wafers, metal plates, polymer films (plates), paper, etc. to form a film for use. Is also possible.

  The binder which can be used by mixing with the energy-sensitive ray curable composition of the present invention can be dissolved uniformly without separation of the energy-sensitive ray acid generator (A) and the acid curable compound (B) of the present invention. If possible, there is no particular limitation. Specific examples include polymers or copolymers such as polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, polyvinyl esters, and the like. More specifically, polymethacrylic acid, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, epoxy resin, alkyd resin and others, Akamatsu An industry official described in the supervision of Sei, described in “New Technology of Photosensitive Resins” (CMC, 1987) and “Chemical Products of 10188”, pages 657-767 (Chemical Industry Daily, 1988) Organic polymer of the like. In addition, these binders themselves may have a functional group that can participate in a crosslinking reaction using an acid as a catalyst. In addition, when these polymers are provided with a function such as alkali developability by a substituent represented by a phenolic hydroxyl group or a carboxylic acid group, solubility in an alkali developer is imparted, which will be described later. It can also be applied as a negative resist.

  The energy-sensitive ray-curable composition of the present invention is very rapid for energy rays, particularly light irradiation in the wavelength region of 300 nm to 450 nm without using a sensitizer due to the effect of using the acid generator (A). Although it can be cured reliably, a sensitizer may be used in combination as required.

  Examples of sensitizers that can be used in combination with the present invention include condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, and benzothiazoles. Derivatives, chalcone derivatives and unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, Thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives Thiazine derivatives, phenothiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetra Azaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, anurene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, metal arenes Complex, organic ruthenium complex, etc. Hara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Tadasaburo et al., “Special Functional Materials” (1986, The dyes and sensitizers described in “CMC”, Photopolymer Social Meeting, “Sensitive Material List Book” (1996, published by Bunshin) are not limited to these, and these may be used as necessary. Two or more kinds may be used in any ratio.

  Among these sensitizers, preferred are naphthalene derivatives, condensed polycyclic aromatic derivatives of anthracene derivatives, and phenothiazine derivatives, carbazole derivatives, and benzothiazole derivatives, and particularly preferred are anthracene derivatives. It is done.

  Specific examples thereof include anthracene, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, 9-anthracene carboxylic acid, 9-anthracaldehyde, 9,10-bis (chloromethyl) anthracene, 9,10-bis (phenyl). Ethynyl) anthracene, 9-bromoanthracene, 1-chloro-9,10-bis (phenylethynyl) anthracene, 9-cyanoanthracene, 9,10-dibromoanthracene, 9,10-dicyanoanthracene, 9,10-dimethylanthracene, 9,10-dibutylanthracene, 9,10-diphenylanthracene, 9,10-di-p-tolylanthracene, 9,10-bis (p-methoxyphenyl) anthracene, 2-hydroxymethylanthracene, 9-hydroxymethylanthracene, -Methylanthracene, 9-phenylanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenoxyanthracene, 9,10-dimethoxyanthracene-2-sulfone Acid sodium, 1,4,9,10-tetrahydroxyanthracene, 2,2,2-trifluoro-1- (9-anthryl) ethanol, 1,8,9-trihydroxyanthracene, 1,8-dimethoxy-9, 10-bis (phenylethynyl) anthracene, 9-vinylanthracene, 9-anthracenemethanol, trimethylsiloxy ether of 9-anthracenemethanol, phenothiazine, N-ethylcarbazole, N-phenylcarbazole, 1-methoxynaphthalene, 2- Toki naphthalene. Examples include 1,4-dimethoxynaphthalene.

  Although the addition amount in the case of using the said sensitizer together is not specifically limited, 0-100 weight part is preferable with respect to 100 weight part of energy-sensitive linear acid generators of this invention.

  The energy-sensitive acid generator (A) of the present invention has sufficiently high sensitivity as an acid generator, but can be used in combination with other acid generators. The acid generator that can be used in combination with the energy-sensitive linear acid generator (A) is not particularly limited, and “PAG”, “acid generator”, “photoacid generator”, “photopolymerization initiator”, “ Materials known in the industry under names such as “cationic polymerization initiator” and “polymerization catalyst” can be appropriately selected and used. Moreover, when using another acid generator, it is also possible to use individually or in combination.

  Examples of other energy sensitive acid generators that can be used in combination with the energy sensitive acid generator of the present invention include onium salt compounds. Examples of such onium salt compounds include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, diazonium salt compounds, pyridinium salt compounds, benzothiazolium salt compounds, sulfoxonium salt compounds, and ferrocene compounds. These structures are not particularly limited, and may have a polyvalent cation structure such as a dication, and known counter anions can be appropriately selected and used.

  Examples of the energy-sensitive linear acid generator other than the onium salt that can be used in combination with the energy-sensitive linear acid generator of the present invention include nitrobenzyl sulfonates, alkyl or aryl-N-sulfonyloxyimides, and halogenated compounds. Alkylsulfonic acid esters, 1,2-disulfones, oxime sulfonates, benzoin tosylates, β-ketosulfones, β-sulfonylsulfones, bis (alkylsulfonyl) diazomethanes, iminosulfonates Compounds having a trihaloalkyl group, such as imide sulfonates, trihalomethyltriazines, and the like, but are not limited thereto.

  The ratio of the other acid generator used in combination with the energy-sensitive linear acid generator (A) of the present invention is not particularly limited, but is in the range of 0 to 99 parts by weight with respect to 100 parts by weight of the acid generator (A) of the present invention. Is preferably used.

  The curable composition using the energy-sensitive linear acid generator of the present invention can be used by dissolving it in a solvent that dissolves each of the above components and coating it on a support. The solvent used here is not particularly limited as long as it can uniformly dissolve the energy-sensitive ray curable composition of the present invention. Specific examples include 1,1,2,2-tetrachloroethane, ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl methoxypropionate, ethyl ethoxypro Pionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, isoamyl acetate, methyl lactate, Ethyl lactate, ethyl ethoxypropionate, N, N monodimethylformamide, N, N monodimethylacetamide, dimethyl sulfoxide, N-methylpyrrole Are preferred, such as down, the use of these solvents alone or in combination.

  Furthermore, additives such as surfactants, antihalation agents, antistatic agents, leveling agents, antifoaming agents and the like can be appropriately mixed and used in the above solvent.

  The solution containing the energy-sensitive ray curable composition of the present invention is applied onto a sheet-like substrate using a roll coater, spin coater, gravure coater, comma coater, bar coater, curtain coater, die coater, inkjet printer, etc. A film can be formed by drying this. Although there is no restriction | limiting in what is used by this invention as a sheet-like base material, Porous base materials, such as paper, a nonwoven fabric, a fabric, a porous glass sheet, or synthetic paper, a coated paper, a polymer film, metal foil, etc. It is possible to use a base material or the like. These substrates may be used alone or in the form of a laminated composite substrate. Further, a protective film such as a polymer film can be further provided for the purpose of protecting the film of the cured product layer thus formed.

  The energy-sensitive ray-curable composition containing the energy-sensitive ray acid generator (A) and the acid-curable compound (B) of the present invention is sensitive to energy rays, particularly when irradiated with light in the wavelength region of 300 nm to 450 nm. The acid generated efficiently from the energy ray acid generator (A) can be easily cured, and a cured product having good characteristics can be obtained.

  The energy ray source used to cure the acid curable composition of the present invention is not particularly limited, but the energy sensitive acid generator (A) emits light in a wavelength region of 300 nm to 450 nm at which particularly suitable sensitivity is expressed. A light source that can be irradiated is preferable, and other energy rays may be emitted simultaneously with the light in the wavelength region. A particularly preferable light source is a light source having a main wavelength of light emission in a wavelength region of 300 nm to 450 nm. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, and a xenon. Examples include, but are not limited to, lamps and pulsed light xenon lamps. Also suitable are lasers having an emission wavelength in the wavelength region of 300 nm to 450 nm, such as Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, and semiconductor excitation solid laser. It can be used as an energy ray source. An electron beam can also be used as a suitable energy beam source. All of the energy-sensitive acid generators (A) of the present invention have suitable absorption in the wavelength region of 300 nm to 450 nm and the absorption characteristics are slightly different depending on the substituent, but by appropriately selecting the light source described above, It can function as a highly sensitive energy-sensitive linear acid generator. In addition, these light sources can appropriately irradiate the energy-sensitive ray-curable composition of the present invention through optical devices such as filters, mirrors, and lenses.

  The energy-sensitive ray-curable composition of the present invention can be cured by heating at the same time as the energy ray irradiation from the energy ray source or after the energy ray irradiation to obtain a cured product having good characteristics. It is.

  When the energy-sensitive ray curable composition of the present invention is cured, the solubility to an organic solvent or an alkali developer is lowered in the portion irradiated with the energy rays. For this reason, if the pattern is exposed through a pattern mask that partially transmits energy rays, or if the pattern is directly drawn by a laser and then developed with an organic solvent or alkaline developer, the portion irradiated with energy rays It can be left as an insolubilized pattern, and can be used as a so-called negative resist material. Examples of the use of such a resist include negative photoresists such as a photosensitive printing plate, a color filter resist, a black matrix resist, a semiconductor resist, a solder resist, and a circuit board resist.

  In performing pattern formation using the negative resist as described above, a substrate used in the manufacture of precision integrated circuit elements (eg, silicon / silicon dioxide coating, silicon layer formed on a glass substrate, etc.) ), Substrates used for printed circuits (eg, copper-clad laminates), glass plates (or plastic plates) used for color filters, or substrates used for lithographic printing plates (eg: An anodized Al plate is applied by an appropriate application method such as a spinner or a coater, and then pre-baked under controlled conditions and irradiated with energy rays through a predetermined mask, or a laser ( (Or alternatively, electron beam), and under the controlled conditions, the unirradiated area of the energy beam is selectively removed with a developer. Ri, it is possible to form a good pattern image.

  In addition, for the purpose of diffusing the generated acid in the system or for the purpose of accelerating the curing reaction by the generated acid, it is possible to heat (post-bake) after irradiation with energy rays. . The heating method is not particularly limited, and examples thereof include use of a heating oven and a hot plate. The heating temperature is preferably selected as appropriate depending on the type of acid generator and the type of polymer compound to be used, but is preferably below the decomposition temperature of the acid generator.

  Examples of the developer for developing the negative resist include an organic solvent or an alkali developer. Examples of the organic solvent include the same solvents that can be used to uniformly dissolve the energy-sensitive ray-curable composition of the present invention described above. In addition, the alkaline developer includes the following inorganic or organic base solutions, and these include an acid curable compound used in the curable composition of the present invention or a binder used in combination with a carboxylic acid group or a phenolic hydroxyl group. It is effective when it has an alkali-soluble group such as.

  Specific examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. It is desirable to use aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine. Further, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.

  When the energy-sensitive ray-curable composition of the present invention is partially cured by the same method as described above, there is a difference in optical characteristics represented by the refractive index between the cured portion and the uncured portion. If this principle is used, it can be used as a communication waveguide or an image forming material such as a hologram.

  Other uses of the energy-sensitive linear acid generator of the present invention and the acid catalyst generated from the acid generator include a positive resist material utilizing a catalytic reaction with an acid, particularly a chemically amplified positive type. Resist materials are effective.

  That is, the composition containing the energy-sensitive linear acid generator (A) of the present invention and the compound (C) whose solubility in an alkaline developer is increased by a reaction using an acid as a catalyst is an energy ray, particularly 300 nm to 450 nm. By irradiation with light in the wavelength region, it can be used as an energy sensitive positive resist composition having good sensitivity and dissolution contrast.

  The compound (C) whose solubility in an alkaline developer is increased by the reaction using an acid as a catalyst used in the present invention will be described.

  As used in the present invention, the compound (C) whose solubility in an alkaline developer is increased by an acid-catalyzed reaction includes, for example, carboxylic acid esters, carbonic acid esters, phenolic hydroxyl ethers, alkoxysilanes, and the like. All of these undergo a decomposition reaction or deprotection reaction in which the ester bond, carbon-oxygen bond, or siloxy bond is converted into a carboxyl group, a hydroxyl group, or a silanol group by an acid-catalyzed reaction. This compound increases the solubility in an alkali developer. That is, the compound (C) whose solubility in an alkali developer is increased by an acid-catalyzed reaction refers to an alkali developer having an acidic group such as a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, or a silanol group. In other words, the hydrogen atom of the acidic group of the soluble compound is protected by a protecting group that is easily decomposed in the presence of an acid, and is thus referred to as a hardly alkali-soluble compound that suppresses solubility in an alkali developer. This includes materials known in the industry as materials for the “chemically amplified resist”.

  Typical compounds soluble in an alkaline developer having an acidic group such as a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, or a silanol group are poly-o-hydroxystyrene and poly-m-hydroxystyrene. And poly-p-hydroxystyrene. In addition, a high molecular weight polymer obtained by copolymerizing a monomer selected from p-hydroxystyrene with N-substituted maleimide, maleic anhydride, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, styrene, cycloolefin, and vinyl ether is also developed with alkali. Examples of the compound that are soluble in the liquid include, but are not limited to, and any positive resist material known in the industry can be used.

  The molecular weight of the compound that is soluble in the alkali developer as the raw material of the compound (C) is not particularly limited, but is preferably in the range of 1000 to 100,000 in terms of polystyrene-reduced weight average molecular weight by GPC, from the viewpoint of film formability and coating suitability. Is particularly preferably in the range of 2000 to 50000.

  Protective groups that can be easily decomposed in the presence of an acid used to suppress the solubility of an alkali developer in a compound that is soluble in the above alkali developer include a methoxymethyl group, an ethoxyethyl group, t -Alkoxyalkyl groups represented by butoxymethyl group, isopropoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-isopropoxyethyl group, 1-ethoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group , T-butoxycarbonyloxymethyl group, alkoxycarbonyloxyalkyl group represented by 1-methyl 1-phenylethoxycarbonyloxymethyl group, t-butyl group, t-pentyl group, 1-methyl-1-phenylethyl group, etc. Tertiary alkyl group, trimethylsilyl group, ethyldimethylsilyl group represented by And the like can be mentioned trialkylsilyl group typified t- butyldimethylsilyl group, but is not limited thereto.

  When protecting an acidic group present in a compound that is soluble in an alkaline developer with a protective group that is easily decomposed by the presence of an acid, a sufficient alkaline developer is required without protecting all of the acidic groups. The effect of inhibiting the dissolution of the protective group is 10% to 100% when the number of acidic groups present in the compound soluble in the alkaline developer is 100%. It is preferable to protect the acidic group of with a protective group. If the introduction ratio of the protecting group is less than 10%, a sufficient dissolution inhibiting effect in the alkali developer cannot be obtained, and the compound (C) whose solubility in the alkali developer is increased by the reaction using the acid of the present invention as a catalyst. ) Does not work as well.

  These compounds (C) whose solubility in an alkaline developer is increased by a reaction using an acid as a catalyst can be used alone or in combination. Moreover, it can also be used by mixing with other alkali-soluble resins such as phenolic novolac resins.

  The composition containing the energy sensitive acid generator (A) of the present invention and the compound (C) whose solubility in an alkaline developer increases by an acid-catalyzed reaction is an energy ray, particularly a wavelength of 300 nm to 450 nm. By the light irradiation of the region, an acid is efficiently generated from the acid generator (A). Using this acid as a catalyst, the compound (C) having a low solubility in an alkali developer before irradiation with energy rays. ) Is easily decomposed, and as a result, the solubility of the compound (C) in the alkali developer is greatly increased. Therefore, when energy rays are irradiated through a mask that has a characteristic of being partially irradiated with energy rays, or when a pattern is directly drawn with a laser or the like, only the portion to which the energy rays are applied is soluble in an alkaline developer. Therefore, when developing with an alkaline developer, a so-called positive resist pattern can be formed. The positive resist composition using the present invention realizes good resist sensitivity by the acid generated efficiently from the acid generator (A), and has high solubility in the part irradiated with the energy beam and the part not irradiated. It is possible to produce a difference, i.e. a dissolution contrast.

  The compounding ratio of the energy-sensitive linear acid generator (A) to the compound (C) whose solubility in an alkaline developer is increased by an acid-catalyzed reaction is not particularly limited, but with respect to 100 parts by weight of the compound (C), It is preferable to use the energy sensitive acid generator (A) in a ratio of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

  The positive resist composition using the present invention includes t-butyl esters, t-butyl carbonates, t-butyl ethers of aromatic compounds [Proc. SPIE, 920, p60 (1988), Polym. Eng. Sci. 29, 846 (1989)], polyhydroxy compounds protected with a tetrahydropyranyl group [JP-A-1-67500], and other acetal compounds [Polym. Eng. Sci. 29, 874 (1989)] and the like can also be used. In addition, an amine-based compound can be added to the positive resist composition utilizing the present invention in order to improve environmental resistance and control the pattern shape.

  Such a positive resist composition may further contain a dye or the like as necessary for the purpose of coloring or the like. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (orientated chemistry) Kogyo Co., Ltd.), crystal violet (CI-42555), methyl violet (CI-42535), rhodamine B (CI-45170B), malachite green (CI-422000), methylene blue (CI-52015) and the like. .

  The positive resist composition using the energy-sensitive linear acid generator of the present invention as described above can be used by dissolving it in a solvent that uniformly dissolves each of the above components and coating it on a support. The solvent used here is not particularly limited as long as it can dissolve the positive resist composition uniformly. Specific examples include 1,1,2,2-tetrachloroethane, ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl methoxypropionate, ethyl ethoxypro Pionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, isoamyl acetate, methyl lactate, Ethyl lactate, ethyl ethoxypropionate, N, N monodimethylformamide, N, N monodimethylacetamide, dimethyl sulfoxide, N-methylpyrrole Are preferred, such as down, the use of these solvents alone or in combination.

  Furthermore, additives such as surfactants, antihalation agents, antistatic agents, leveling agents, antifoaming agents, and light absorbers for adjusting the absorbance can be appropriately mixed and used in the above solvent. is there.

  The positive resist composition utilizing the present invention has sufficient sensitivity by using the energy-sensitive linear acid generator (A), but is used in combination with other acid generators and sensitizers. It is also possible. Examples of such other acid generators and sensitizers include the same materials as those described in the section of the energy-sensitive ray curable composition of the present invention.

  In pattern formation using the positive resist composition as described above, a substrate (eg, silicon / silicon dioxide coating, silicon layer formed on a glass substrate) used in the manufacture of precision integrated circuit elements is used. Etc.), substrates used for printed circuits (eg, copper-clad laminates), glass plates (or plastic plates) used for color filters, or substrates used for lithographic printing plates (eg, : Anodized Al plate) by an appropriate coating method such as spinner or coater, pre-baked under controlled conditions, and irradiated with light (or electron beam) through a predetermined mask. Or after direct drawing with a laser (or electron beam), under controlled conditions, the irradiated area is developed and selectively removed, It is possible to form a good pattern image.

  As the energy beam source for irradiating the positive resist composition utilizing the present invention, the same energy beam sources as those enumerated in the description of the curable composition of the present invention can be used. Further, reduction projection exposure using a stepper is also possible.

  In addition, for the purpose of diffusing the generated acid in the system or for the purpose of promoting the deprotection reaction with the generated acid, it is possible to heat after irradiation with energy rays. As a heating method, a heating oven, a hot plate, or the like can be used. This method enables so-called chemical amplification. The heating temperature is preferably selected as appropriate depending on the type of acid generator and the type of polymer compound to be used, but is generally in the range of 40 ° C to 160 ° C.

  The alkaline developer for developing the positive resist composition using the present invention includes the following inorganic or organic base solutions, which are the reactions described above using an acid as a catalyst. Is used to dissolve and remove the compound (C) whose solubility in an alkaline developer is changed to a carboxyl group, a hydroxyl group, a silanol group, or the like by a reaction using an acid as a catalyst.

  Examples of suitable developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide It is desirable to use aqueous solutions of alkalis such as quaternary ammonium salts such as pyrrole, cyclic amines such as piperidine, and the like. Further, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.

  As another application using the energy-sensitive linear acid generator of the present invention, a coloring material utilizing a coloring reaction with an acid can be mentioned.

  The composition containing the energy-sensitive linear acid generator (A) of the present invention and the dye precursor (D) that develops color by the reaction of an acid is rapidly and rapidly irradiated by energy rays, particularly light irradiation in the wavelength region of 300 nm to 450 nm. It can function as an energy-sensitive color-developing composition having a good color density.

  The dye precursor (D) that develops color by reaction with the acid used in the present invention will be described. Examples of the dye precursor that can be used in the present invention include already known dye precursors such as triphenylmethane dyes, trimethanephthalide dyes, phenothiazine dyes, phenoxazine dyes, fluorane dyes, indolylphthalide dyes, Examples include azaphthalide dyes, diphenylmethane dyes, chromenopyrazole dyes, leucooramine dyes, rhodamine lactam dyes, azomethine dyes, and leucoxanthene dyes.

  Specific examples of these dye precursors (D) include JP-A-59-190891, JP-A-60-202155, JP-A-62-167086, and JP-A-61-51381. JP-A-60-184878, JP-A-50-195173, JP-A-62-27171, JP-A-62-210664, JP-A-62-24752, JP-A-61-1 -230981, JP-A 61-101556, JP-A 62-84157, JP-A 56-52759, JP-A 60-196177, JP 58-7453, JP 58-76458, JP 59-135254, JP 55-265, JP 52-82243, 57-195155, JP 6 JP-A-74961, JP-A-63-236679, JP-A-sho, JP-A-58-209589, JP-A-62-179983, JP-A-63-317558, JP-A-sho No. 49-103710, JP-A-63-251278, JP-A-63-251279, JP-A-63-251280, JP-A-51-8012, JP-A-58-192877. JP-A-58-192858, JP-A-62-77132, JP-A-54-126114, JP-A-64-251148, JP-A-47-460110, JP-A-61. JP-A-195164, JP-A-61-230981, JP-A-63-270662, JP-A-53-90255, JP-A-63-199268 JP 51-121035, JP 55-115448, JP 58-157779, JP 61-87758, JP 62-243652, JP 61-61. JP 1113589, JP 62-176881, JP 60-23890, JP 48-95420, JP 59-162086, JP 62-198495, JP 59-199775, JP 64-511978, JP 62-127353, JP 62-292859, JP 50-124930, JP 54-1111528. JP, 49-59127, JP 52-92618, JP 50-137549, JP 54-61637, JP 59-25393, JP-A 53-97512, JP-A 62-94841, JP-A 62-198494, JP 64-3176 JP 46-16052, JP 51 -92207, JP-B 48-43296, JP-B 51-23204, JP-B 52-10871, JP-B 58-40991, JP-B 51-15445, JP-B 60-27692 Gazette, JP-B 54-26929, JP-B 55-49086, JP-B 56-162690, JP-B 46-4614, JP-B 47-20479, JP-B 47-42364 Japanese Patent Publication No. 60-1341, Japanese Patent Publication No. 59-30748, Japanese Patent Publication No. 47-1179, Japanese Patent Publication No. 45-4698 JP-B-46-16053, JP-B-49-3047, JP-B-45-8557, JP-B-61-12852, JP-B-56-12515, JP-B-64-2589, Japanese Patent Publication No. 46-22649, Japanese Patent Publication No. 54-25445, Japanese Patent Publication No. 47-19799, Japanese Patent Publication No. 51-23202, Japanese Patent Publication No. 55-7473, Japanese Patent Publication No. 56-11596, Japanese Patent Publication No. 57 No. 24233, Japanese Patent Publication No. 60-25275, Japanese Patent Publication No. 60-23991, Japanese Patent Publication No. 51-92207, Japanese Patent Publication No. 48-18725, Japanese Patent Publication No. Sho 61-25745, Japanese Patent Publication No. 51-16807 Gazette, JP-B 63-43398, JP-B 42-25654, JP-B 59-3279, JP-B 60- No. 794, JP-B-50-14532, JP-B 37-4041, JP-B 46-12248, JP-A-4-224990, JP-A-4-225882, JP-A-4-18060. JP-A-2-26789, JP-A-3-143680, JP-A-3-294280, JP-A-2-58574, JP-A-3-127794, JP-A-1-190484, JP-A-2-26783, JP-A-4-223467, JP-A-1-213636, JP-A-1-160979, JP-A-1-264889, JP-A-2-135264, JP-A-2 No. 2-339987, Japanese Patent Laid-Open No. 2-26782, Japanese Patent Publication No. 4-60035, US Pat. No. 4,444,591, US US Pat. No. 4,515,971, US Pat. No. 4,341,403, US Pat. No. 3,560,229, US Pat. No. 4,436,920, US Pat. No. 4,390,616, US Pat. No. 4,775,656, US Pat. No. 3,514,310, US Pat. No. 2,417,897, US Pat. No. 2,548,366, US Pat. No. 2,505,472, US Pat. No. 4,420,356, US Pat. No. 4,057,562, US Pat. No. 4,320,636 US Pat. No. 4,505,093, US Pat. No. 4,562,449, US Pat. No. 3,873,573, US Pat. No. 4,119,777, US Pat. No. 4,795,736, US Pat. No. 4,794,609 U.S. Pat. No. 3,787,412 Description, U.S. Pat. No. 4,820,841, U.S. Pat. No. 4,598,150, U.S. Pat.No. 4,446,321, British Patent 1,339,316, British Patent 1,160,940, European Patent 4,330,024, etc. The material currently disclosed by the well-known literature can be used.

  It is preferable to further add a polymer binder to the energy-sensitive color-developing composition of the present invention. Such a polymer binder is not particularly limited, has compatibility with the energy-sensitive linear acid generator (A) and the dye precursor (D) of the present invention, and can be dissolved and applied in an appropriate solvent. Yes, and desirably there is no particular problem as long as it is a thermoplastic polymer compound, but residues such as a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, and a silanol group that can induce color development of the dye precursor (D) are present. The polymer compound which does not have is preferable. The minimum content of these functional groups is preferably selected as appropriate.

  Specific examples of the polymer binder include polystyrene, styrene / acrylic acid ester copolymer, styrene / methacrylic acid ester copolymer, polyacrylic acid esters such as polymethyl acrylate and polyethyl acrylate, and polymethacrylic acid. Polymethacrylates such as methyl acid and polyethyl methacrylate, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyurethane, bisphenol A (or tetrabromobisphenol A, bisphenol F, bisphenol S, etc.) type epoxy resin, Novolak type epoxy resin, cellulose acetate, cellulose acetate succinate, cellulose derivatives such as methyl cellulose, ethyl cellulose, polyvinyl butyral, polyvinyl formal, polyamide resin, polyester Resin, and the like can be mentioned alkyd resin.

  The energy sensitive color forming composition using the present invention has sufficient sensitivity by using the energy sensitive acid generator (A), but other acid generators and sensitizers are used in combination. Can also be used. Examples of such other acid generators and sensitizers include the same materials as those described in the section of the energy-sensitive ray curable composition of the present invention.

  When the thus obtained energy-sensitive ray-coloring composition is used as an energy-sensitive ray-coloring composition in which a film is formed on a sheet-like substrate, the composition is dissolved in a solvent to form a substrate. The method of applying on top can be taken. The solvent used here is not particularly limited. For example, ketone solvents such as MEK, MIBK, cyclohexanone, cyclopentanone, acetate solvents such as ethyl acetate, amyl acetate (or isoamyl), butyl acetate, and lactic acid. Lactic acid esters such as methyl and ethyl lactate, halogen solvents such as 1,1,2,2-tetrachloroethane and ethylene dichloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl Glycol acetate solvents such as ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, aromatic solvents such as toluene and xylene, N, N monodimethylformamide, , N one dimethylacetamide, preferably such as dimethylsulfoxide, using these solvents singly or in combination. A method of transferring the composition once formed on the substrate to another substrate by a thermal transfer method or the like to prepare a color forming composition can also be selected.

  Furthermore, additives such as a surfactant, an antihalation agent, an antistatic agent, a leveling agent, and an antifoaming agent can be appropriately mixed and used in the above solvent.

  Although there is no restriction | limiting in particular in the compounding ratio of said energy sensitive ray coloring composition, Preferably, the content rate of an energy sensitive acid generator (A) in this composition is the range of 0.1 to 40 weight%, The content of the dye precursor (D) is in the range of 0.1 to 40% by weight, and when the polymer binder is used, the content can be blended in the range of 10 to 95% by weight. In particular, the visibility of the dye precursor (D) is increased by adjusting the maximum color density so that the optical density is at least 0.5 or more, more preferably 1.0 or more in terms of optical density (Optical Density). Desirable for.

  The solution containing the energy-sensitive color-developing composition of the present invention prepared in this way is a sheet using a roll coater, spin coater, gravure coater, comma coater, bar coater, curtain coater, die coater, inkjet printer, etc. A film can be formed by applying on a substrate and drying it. Although there is no restriction | limiting in what is used by this invention as a sheet-like base material, Porous base materials, such as paper, a nonwoven fabric, a fabric, a porous glass sheet, or synthetic paper, a coated paper, a polymer film, metal foil, etc. It is possible to use a base material or the like. These substrates may be used alone or in the form of a laminated composite substrate. Further, a protective film such as a polymer film can be further provided for the purpose of protecting the film of the energy-sensitive color-developing composition layer thus formed.

  The energy-sensitive color-developing composition of the present invention prepared as described above is irradiated with energy rays through a predetermined mask (negative mask) or directly drawn using a laser beam (or electron beam beam). As a result, a good pattern image having a high color density can be obtained by causing partial color development. In addition, in order to sufficiently diffuse the acid generated from the acid generator (A) and promote the reaction with the dye precursor (D), it is possible to heat at the same time as energy beam irradiation or after energy beam irradiation. is there.

The energy ray source used for color development of the energy sensitive ray coloring composition of the present invention is not particularly limited, but in the explanation of the energy sensitive ray curable composition and the energy sensitive positive resist composition described above. It is possible to use energy sources similar to those listed.

The structures of the energy sensitive acid generator and sensitizer used in Examples and Comparative Examples of the present invention are shown below.

(Synthesis Example 1)
Synthesis of Compound (1) 30 ml of dichloromethane was cooled to 0 ° C., and 1.54 g of silver perchlorate and 0.93 g of dimethyl sulfide were added. To this solution, a solution of 2.00 g of 4-bromomethyl-7-methoxycoumarin dissolved in 250 ml of dichloromethane was added dropwise over about 1 hour, stirred at 0 ° C. for 1 hour, returned to room temperature, and refluxed for about 10 hours. did. After cooling this solution, the produced solid was filtered off and washed with about 150 ml of acetonitrile, and the resulting washing solution was mixed with the previous filtrate. Crystals obtained by adding 500 ml of diethyl ether dropwise to this solution were filtered to obtain 1.56 g of sulfonium perchlorate (yield 60%).
1.50 g of this sulfonium perchlorate is dissolved in 140 ml of acetonitrile, 62 g of an aqueous solution of 4.6 wt% sodium tetrakis (pentafluorophenyl) borate salt is added dropwise over about 15 minutes and stirred for 1 hour, followed by ion-exchanged water. 1000 ml was added dropwise over 1 hour. The solution was filtered, and the resulting solid was washed thoroughly with ion-exchanged water and then dried under reduced pressure. This solid was recrystallized from dichloromethane-hexane to obtain 3.61 g of Compound (1) as a white powder (yield 95%).

(Synthesis Example 2 )
The compound (3 ) which is an energy-sensitive linear acid generator of the present invention could be easily synthesized by applying the sulfoniumation reaction and the ion exchange reaction of Synthesis Example 1 described above. Synthesis example 1
The results of elemental analysis of the energy-sensitive linear acid generator of the present invention synthesized in Synthesis Example 2 are shown below .

(Compound 1) Elemental analysis C ₃₇ H ₁₅ B ₁ O ₃ S ₁ F ₂₀
Theoretical value C, 47.76% H, 1.62% S, 3.44%
Measurement C, 47.78% H, 1.63% S, 3.45%
(Compound 3) Elemental analysis C ₃₈ H ₁₇ B ₁ F ₂₀ O ₄ S ₁
Theoretical value C, 47.52% H, 1.78% S, 3.34%
Measured value C, 47.62% H, 1.79% S, 3.38%

Example 1
0.6 mmol of the compound (1) as an energy-sensitive acid generator (A) and 3,4-epoxycyclohexylmethyl-3,4 epoxycyclohexanecarboxylate as an acid curable compound (B) (manufactured by Dow Chemical Japan Co., Ltd.) , An alicyclic epoxy monomer, product name UVR-6110), an energy-sensitive linear acid curable composition consisting of 10 g was applied on an aluminum plate with a doctor blade to a thickness of about 10 μm, and light irradiation using a metal halide lamp When an energy beam was irradiated with an apparatus (3 kW, 2 lights) at a conveyor speed of 15 m / min, a good tack-free cured film was obtained.

Example 2 Comparative Example 1 to Comparative Example 5
Except that 0.6 mmol of the energy-sensitive linear acid generator (A) in Example 1 was replaced with 0.6 mmol of the acid generator shown in Table 1, light irradiation was performed in exactly the same manner as in Example 1. Carried out,
The film tack after light irradiation was evaluated. The tack was evaluated in three stages and shown together in Table 1.

Example 4
0.08 mmol of the compound (1) as the energy-sensitive linear acid generator (A) and 3,4-epoxycyclohexylmethyl-3,4 epoxycyclohexanecarboxylate as the acid curable compound (B) (manufactured by Dow Chemical Japan Co., Ltd.) , 1 g of cycloaliphatic epoxy monomer, product name UVR-6110), 1 g of polymethyl methacrylate (Aldrich reagent, molecular weight ca.996000) as binder resin, 16 g of cyclohexanone as solvent, 0 mmol of sensitizer (no addition) A uniform coating solution is prepared, and this coating solution is applied onto a stainless plate polished by # 600 using a spin coater, and then heated in an oven at 40 ° C. for 15 minutes to remove the solvent and remove a 2 μm film. A thick coating film was formed. The coating film is 6 mW / cm ² through a band-pass filter that selectively transmits only 365 nm light from a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. and an ND filter for adjusting the amount of light. Irradiated with intensity. During this light irradiation, an absorption intensity of 789 cm ⁻¹ corresponding to the characteristic absorption of the epoxy group of the coating film on the stainless steel plate is monitored using a reflective IR (Magna 560 FTIR, Rapid Scan Mode, manufactured by Thermo Nicolet). did. From the change in absorption intensity over time, the consumption rate of the epoxy monomer based on the intensity of the characteristic absorption before light irradiation was calculated. After 10 seconds of light irradiation, the consumption rate of epoxy monomer was 12%, and light irradiation was 30 seconds. Later, the consumption rate was 42%.

(Example 5 and Comparative Examples 6 to 12)
Except that 0.08 mmol of the energy-sensitive linear acid generator (A) in Example 4 was replaced with 0.08 mmol of the acid generator shown in Table 2, and the sensitizer was replaced with the compounds and addition amounts shown in Table 2. An experiment was performed in exactly the same manner as in No. 4, and the consumption rate of the epoxy monomer was calculated. Results are also in Table 2
It was shown together.

(Example 7)
Protect 74% of phenolic hydroxyl groups in poly-p-hydroxystyrene (molecular weight 8000) with 1-ethoxyethyl group (acetalization) as compound (C) whose solubility in an alkaline developer is increased by an acid-catalyzed reaction. 1 g of the resulting resin, 0.05 mmol of compound (1) as the energy-sensitive acid generator (A), and 9 g of propylene glycol monomethyl ether acetate (PGMEA) as the solvent are mixed until uniform, and a coating solution for positive resist is prepared. It was adjusted. This coating solution was applied onto a stainless plate polished with # 600 using a spin coater and heated on a hot plate at 90 ° C. for 90 seconds to form a 0.5 μm film. The coating film was irradiated with light from a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. via a band-pass filter that selectively transmits only 365 nm light and an ND filter for adjusting the light amount. During light irradiation, using a reflective IR (Magna 560 FTIR, Rapid Scan Mode, manufactured by Thermo Nicolet Co., Ltd.), the progress of the deprotection reaction of the acetal group by the acid generated by this light irradiation is shown on the coating film on the stainless steel plate. Was monitored as an attenuation of 947 cm ⁻¹ corresponding to the characteristic absorption of the acetal group. From the change over time in the characteristic absorption intensity, the deprotection rate of the acetal group was calculated based on the intensity of the characteristic absorption before the light irradiation. After 10 seconds of light irradiation, the deprotection rate of the acetal group was 21%, After 30 seconds of light irradiation, the deprotection rate was 70%.

(Example 8 and Comparative Examples 13 to 19)
An experiment was carried out in exactly the same manner as in Example 7 except that 0.05 mmol of the energy sensitive acid generator (A) in Example 7 was replaced with 0.05 mmol of the acid generator shown in Table 3, and the acetal group was removed. The protection rate was evaluated. The results are shown in Table 3.

(Example 11)
0.08 mmol of the compound (1) as the energy sensitive acid generator (A), 0 mmol (no addition) of the sensitizer, and 3,4-epoxycyclohexylmethyl-3,4 epoxy epoxy as the acid curable compound (B) 1 g of carboxylate (manufactured by Dow Chemical Japan Co., Ltd., alicyclic epoxy monomer, product name UVR-6110), 1 g of polymethyl methacrylate (Aldrich reagent, molecular weight ca.996000) as a binder resin, cyclohexanone as a solvent A uniform coating solution consisting of 16 g was prepared. This coating solution was coated on a glass plate with a spin coater and dried at 40 ° C. for 10 minutes to form a coating film having a thickness of 1.5 μm. A step tablet (Gray scale film manufactured by Dainippon Screen Co., Ltd.) is placed on this coating film, and the light of a 500 mW high-pressure mercury lamp manufactured by Ushio Electric is exposed for 30 seconds through a heat ray cut filter, and then in toluene for 60 seconds. Development was carried out by impregnation, and the number of stages completely cured and insolubilized corresponding to the step tablet was evaluated as sensitivity. As a result, the sensitivity was 15 stages.

(Example 12, and Comparative Examples 20 to 26)
The acid generator 0 shown in Table 4 was 0.08 mmol of the energy-sensitive linear acid generator (A) of Example 11.
. Example 11 except that 08 mmol and the sensitizer were replaced with the compounds and addition amounts shown in Table 4.
The number of sensitivity steps was evaluated by exactly the same operation. The experimental results are also shown in Table 4.

(Example 14)
0.04 mmol of the compound (1) as the energy-sensitive acid generator (A), 0 mmol (no addition) of the sensitizer, 0.04 mmol of crystal violet lactone as the dye precursor (D) that develops color by acid, and poly as the binder A uniform coating solution was prepared by mixing 1 g of methyl methacrylate (reagent manufactured by Aldrich, molecular weight ca.996000) and 9 g of cyclohexanone as a solvent. This coating solution was applied with a spin coater on a glass plate and dried at 40 ° C. for 15 minutes to form a coating film having a thickness of 6 μm. For this coating film, a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. is passed through a band-pass filter that selectively transmits only 365 nm light and an ND filter for adjusting the amount of light. When irradiated for 4 seconds at an intensity of cm ² , a blue color was observed in the irradiated area. When the absorption spectrum of the coating film after light irradiation was measured and the absorbance at 608 nm corresponding to the absorption maximum wavelength of the colored dye was measured, the absorbance was 0.13.

(Example 15, and Comparative Example 27 to Comparative Example 33)
Except that 0.04 mmol of the energy-sensitive linear acid generator (A) in Example 14 was changed to 0.04 mmol of the acid generator shown in Table 5, and the sensitizer was changed to the compounds and addition amounts shown in Table 5, Exactly the same experiment as in Example 14 was performed, and the color density of the dye at 608 nm after light irradiation was evaluated. The results are shown in Table 5.

  The present invention provides an energy sensitive acid generator that functions as an acid generator having a very high sensitivity to irradiation with energy rays, particularly irradiation with light of 300 to 450 nm. Therefore, the acid generator of the present invention can rapidly and reliably proceed with polymerization, crosslinking, decomposition, color development reaction, etc. using the acid generated by irradiation of energy rays, which has been used conventionally, as a result. Higher sensitivity to energy rays for various uses, or improvement of characteristics for various uses due to sufficient progress of the reaction can be expected. Examples of applications that can be expected to improve sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-forming resins, sealants, dental polymerization materials, printing inks that utilize polymerization or crosslinking reactions, Paint, Photosensitive resin for printing plates, Color proof for printing, Color filter resist, Black matrix resist, Printed circuit board resist, Semiconductor manufacturing resist, Microelectronics resist, Micromachine parts manufacturing resist, Insulating material, Hologram Materials, waveguide materials, overcoat agents, adhesives, pressure-sensitive adhesives, adhesives, release coating agents, etc., or image formation methods using coloring reactions of dye precursors using the generated acid as a catalyst, forgery prevention Method, energy dose detection method, etc., for semiconductor manufacturing using decomposition reaction catalyzed by generated acid, T T for producing a color filter for producing, positive resist materials such as for micromachine component manufacturing and the like.

Absorption spectrum of compound (1) and compound (2) (acetonitrile)

Claims (5)

An energy sensitive acid generator represented by the following general formula (1).
General formula (1)

(Wherein R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group) Represents a group, an alkoxycarbonyloxy group, an amino group, or a halogen atom.
Provided that at least one of R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ is

Represents. R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group.
However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₀₆ , R ₁₁ , R ₁₂ , R ₂₁ , and R ₂₂ may be combined to form a ring.
X ⁻ is a borate represented by the following general formula (2) . )
General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group
A phenyl group substituted by two or more groups,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. ) R ₀₂ is

The energy-sensitive linear acid generator according to claim 1. A method for generating an acid, comprising generating an acid by irradiating the energy-sensitive acid generator according to claim 1 or 2 with light in a wavelength region of 300 nm to 450 nm. An energy sensitive ray curable composition comprising the energy sensitive acid generator (A) according to claim 1 or 2 and an acid curable compound (B). The manufacturing method of hardened | cured material which irradiates and cures the energy-sensitive-ray-curable composition of Claim 4 by irradiating the energy ray containing the light of the wavelength range of 300 nm to 450 nm.

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