JP2007231235A - Photocurable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition not effected with inhibition of oxygen in air, containing no corrosive substance such as generated strong acid, progressing reaction highly efficiently, and increased in solubility of the composition mixture thereof so that the curing technology for promptly solidifying a liquid by using active energy rays such as light is improved in technical advantages. <P>SOLUTION: The photocurable resin composition essentially contains a photo-base generator (A) generating a base by light and containing, as a substituent for alkoxysilane, at least one substituent selected from acyloxyimino, N-formylated aromaticamino, N-acylated aromaticamino, nitrobenzylcarbamate, and alkoxybenzylcarbamate, and an alkoxysilane (B) having a functional group reacting with generated base. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition comprising a photobase-generating siloxane compound that generates a base by light, a siloxane compound that reacts with the base, and a base-proliferating siloxane compound, and a photocurable resin composition that is a condensation polymer thereof. Is.

  Resin or its composition that feels as an activation energy ray can be used for resist materials, chemical structural changes caused by the action of heat, light, infrared rays, far infrared rays, electron beams, X-rays, etc. It has been put to practical use in many fields, such as using curing for surface coating. Of the activation energy rays, light is widely used. Hereinafter, the activation energy rays are specified and described as light. However, the activation energy rays for the resin of the present invention or its composition are limited to light. Is not to be done. In recent years, photosensitive resin compositions using an acid generated by light as a catalyst or a polymerization initiator have been applied to various fields such as photoresist materials and photocuring materials.

  In a chemically amplified resist material, a strong acid generated by activation energy rays is used as a catalyst, and a resin component is chemically modified to cause a change in solubility to form a pattern. A wide variety of resist materials have been developed. In order to function adequately as a resist material, it is indispensable that the patterned film has etching resistance as well as high resolution and high sensitivity. As a resin suitable for an ultraviolet resist material, a material having resistance to oxygen plasma etching is required. On the other hand, various attempts have been made so far in order to improve the curing rate of monomers, oligomers and polymers by light. The most widely developed object is a photopolymerization system in which a large number of vinyl monomers are chain-polymerized using a radical species generated by the action of light as an initiator. In addition, a cationic polymerization system in which an acid is generated by the action of light and this acid is used as a catalyst is also an object of active development. However, in the case of a radical polymerization system, since the polymerization reaction is inhibited by oxygen in the air, especially in the thin film system, since curing is suppressed, a special device for blocking oxygen is required. On the other hand, the cationic polymerization system is advantageous in that it does not have such an oxygen-inhibiting effect, but the strong acid generated from the acid generator remains after curing, so that there is a problem with its corrosivity and the possibility of modification of the resin. As pointed out.

  Thus, in order to obtain a highly sensitive photosensitive material with excellent etching resistance as a resist material, and to further improve the performance of a curing technology that rapidly solidifies a liquid using activated energy rays. Therefore, there has been a strong demand for a resin composition that does not receive an inhibitory effect due to oxygen in the air, does not contain a corrosive substance such as a strong acid to be generated, and further allows the reaction to proceed with high efficiency. As one method for overcoming such problems, it has been proposed to use a polymerization reaction or a chemical reaction using a base catalyst. For example, there is a method in which a base is generated by the action of light and the resin is chemically modified using this as a catalyst. For example, since a compound having an epoxy group causes a crosslinking reaction by the action of a base, an amine as an initiator or a catalyst is generated in the epoxy resin layer by the action of light or heat, and then cured by heat treatment or the like. There is. However, since the curing rate due to the action of activation energy rays is low, it has not been put to practical use.

  In order to overcome this problem, a base proliferation reaction has been proposed in order to secondarily enhance basic compounds generated by the action of light (Non-Patent Documents 1, 2, and 3). Furthermore, an activation energy ray composition containing a base proliferating agent composed of a certain urethane compound exhibiting this base proliferating reaction has been proposed (Patent Documents 1 and 2). That is, since the base generated in this base growth reaction is mainly a primary or secondary aliphatic amine, the basic growth agent that generates these amines is based on the combination of a photobase generator and a base-reactive substance. A photosensitive resin composition is obtained. In order to carry out this base multiplication reaction efficiently, heat treatment is usually required. For this reason, amine generated in the growth reaction is evaporated and scattered in the course of heat treatment in an open system, for example, amine curing of epoxy resin. There is a disadvantage that the effect of adding a sufficient base proliferating agent is not recognized in the case of performing. In addition, the urethane-based compound generally has poor solubility in an organic solvent, and has, for example, a drawback that it does not have sufficient solubility in a liquid epoxy compound having a relatively low polarity. Furthermore, when used as a resist material, the base proliferating agent itself is also required to have etching resistance, and Patent Document 3 reports that the photosensitivity is improved by a specific siloxane and the etching resistance is improved. not enough.

J. et al. Photopolym. Sci. Technol. , 12, 315 (1999) J. et al. Photopolym. Sci. Technol. , 12, 317 (1999) Angew. Chem. , Int. Ed. 39, 3425 (2000) JP 2000-330270 A JP 2002-128750 A JP 2004-99579 A

  In order to further improve the performance of a curing technology that rapidly solidifies a liquid material using activation energy rays typified by light, the present invention is not affected by the oxygen in the air and is not affected by the generated strong acid. It is an object of the present invention to provide a resin composition that does not contain such a corrosive substance, further promotes the reaction with high efficiency, and improves the solubility of the composition mixture.

The inventors of the present application have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention
By light containing at least one substituent selected from acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group and alkoxybenzyl carbamate group as a substituent of alkoxysilane The photobase generator (A) for generating a base and the alkoxysilane (B) having a functional group capable of reacting with the generated base are essential.

In the present invention, the (A) and (B) may be made to have a high molecular weight of 500 to 30,000 by condensation polymerization of alkoxysilane.
Further, the functional group capable of reacting with the base generated by the light of (B) is preferably an oxirane group.
Moreover, it is preferable to contain 10 to 150 parts by weight of the base proliferating agent (C) that generates a base by the action of a base with respect to 100 parts by weight of the total of (A) and (B).
The (C) is preferably a siloxane compound having a substituent of (Formula 1).

（式中、Ｒ¹ およびＲ² は、それぞれ水素、置換基または電子吸引性基を示すが、少なくともその一方は電子吸引性基を示し、Ｒ³ およびＲ⁴ は、それぞれ水素または置換基を示し、Ｚはアミノ基を示す。）

(In the formula, R ¹ and R ² each represent hydrogen, a substituent or an electron-withdrawing group, at least one of which represents an electron-withdrawing group, and R ³ and R ⁴ each represents hydrogen or a substituent. Z represents an amino group.)

In the present invention, (C) and (A) and / or (B) described in claim 1 may be made to have a high molecular weight of 500 to 30,000 by polycondensation of alkoxysilane. .
Moreover, you may contain the epoxy resin (D) further.

  According to the present invention, it is not affected by the oxygen in the air, does not contain a corrosive substance such as a strong acid to be generated, further allows the reaction to proceed with high efficiency, and improves the solubility of the composition mixture. A photocurable resin composition can be obtained. Moreover, the composition of this invention can be used suitably for the coating material, adhesive agent, etc. in each field | area.

The photobase generator in the present invention generates an amine by light and reacts with an epoxy resin with high efficiency by a base proliferating agent. In order to further improve the reactivity, photosilane generator and oxirane group, photobase generator and base proliferator, photobase generator, base proliferator and oxirane group by polycondensation of alkoxysilane by condensation of alkoxysilane. To exist in.
[Photobase generator (A)]
The photobase generator in the present invention is not particularly limited, and a known photobase generator can be used. From the viewpoint of base generation efficiency, an acyloxyimino group, an N-formylated aromatic amino group, N -A photobase generator containing at least one substituent selected from an acylated aromatic amino group, a nitrobenzyl carbamate group and an alkoxybenzyl carbamate group is preferred. These functional groups are photobase generators that become alkoxysilane substituents.
The compound having a photobase generator as a substituent of alkoxysilane in the present invention can be easily obtained by reacting, for example, trialkoxypropyl isocyanate with a compound having a hydroxyl group that generates a base by ultraviolet rays.

[Alkoxysilane (B) having a functional group capable of reacting with a base]
Examples of the alkoxysilane having a functional group capable of reacting with a base in the present invention include alkoxysilanes having an oxirane group, a urethane group, a carboxylic acid group, and the like. Of these, alkoxysilanes having an oxirane group are preferred from the viewpoint of physical properties after curing. The alkoxysilane having an oxirane group of the present invention is not particularly limited, and for example, commercially available compounds such as trimethoxypropyl glycidyl ether and triethoxypropyl glycidyl ether can be used.

  In the present invention, high molecular weight by polycondensation of the photobase generator (A) and the alkoxysilane (B) having a functional group capable of reacting with a base can be obtained easily by ordinary condensation reaction. Can do. Here, high molecular weight is 500-30000, preferably 1000-10000, in terms of workability and compatibility of the photocurable resin composition of the present invention, as a weight average molecular weight. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

[Base proliferating agent (C)]
The base proliferating agent in the present invention is a base proliferating agent that generates a base by the action of a base. For example, those used for chemically amplified photoresists are used (edited by Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (see 1993)). Among these, it is preferable to use a siloxane compound having a substituent of the following formula 1 in order to enhance the compatibility with the photobase generator (A), the epoxy resin (D) described later, and their condensation polymers. .

（式中、Ｒ¹ およびＲ² は、それぞれ水素、置換基または電子吸引性基を示すが、少なくともその一方は電子吸引性基を示し、Ｒ³ およびＲ⁴ は、それぞれ水素または置換基を示し、Ｚはアミノ基を示す。）

(In the formula, R ¹ and R ² each represent hydrogen, a substituent or an electron-withdrawing group, at least one of which represents an electron-withdrawing group, and R ³ and R ⁴ each represents hydrogen or a substituent. Z represents an amino group.)

The siloxane compound having a substituent of formula (1) can be easily obtained by reacting, for example, a trialkoxypropyl isocyanate and a compound having a hydroxyl group having a base-proliferating effect.
In the base-proliferating siloxane compound, the base generated by the action of light increases proliferatively by the base-proliferating reaction, so by adding it to various base-reactive substances, the reaction of the base-reactive substance can be heated or irradiated with light. Can be carried out more efficiently.

  In the present invention, those obtained by increasing the molecular weight of (C) and the above (A) and / or (B) by polycondensation of alkoxysilane can also be used. Here, high molecular weight is 500-30000, preferably 1000-10000, in terms of workability and compatibility of the photocurable resin composition of the present invention, as a weight average molecular weight.

[Epoxy resin (D)]
In this invention, an epoxy resin (D) can be used according to a use in order to improve adhesiveness, adhesiveness, elasticity, etc.
As the epoxy resin in the present invention, a known one is used, but a substance having at least two epoxy groups is preferable. By allowing a base (amine) to act on a compound having at least two epoxy groups, the epoxy compound can be made into a polymer by ring-opening polymerization of the epoxy group. Moreover, the epoxy compound can be chemically modified by adding an amine to the epoxy compound.
Specifically, for example, aliphatic polyvalent glycidyl ether compounds obtained by reaction of polyalkylene glycols with epichlorohydrin, reaction of polyhydric alcohols with epichlorohydrin, aromatic diols or the like such as ethylene glycol, propylene glycol, etc. Examples thereof include aromatic polyvalent glycidyl ether compounds obtained by reacting diols modified with alkylene glycol and epichlorohydrin. An epoxy resin having a siloxane skeleton can also be used for the purpose of improving the compatibility with the siloxane resin. Other specific examples of the epoxy compound exhibiting polymerization reactivity are described in JP 2000-330270 A and JP 2002-128750 A.

[Photocurable resin composition]
Next, the photocurable resin composition of the present invention will be described.
A photocurable resin composition has a photobase generator (A) and an alkoxysilane (B) having a functional group capable of reacting with the generated base as essential components.
In addition, the photocurable resin composition can improve compatibility by introducing an epoxy group and a photobase generator and / or a base proliferating agent into the same polymer, and by modifying the base proliferating agent to siloxane. it can.

In the photocurable resin composition of the present invention, the amount of the photobase generator (A) used is not particularly limited, but is usually based on 100 parts by weight of the alkoxysilane (B) having a functional group capable of reacting with the generated base. 1 to 70 parts by weight, preferably 30 to 60 parts by weight.
The amount of the base proliferating agent (C) used is 10 to 150 parts by weight with respect to 100 parts by weight as a total of (A) and (B).
Moreover, the usage-amount of an epoxy resin (D) is 50-150 weight part with respect to 100 weight part of total of (A) and (C).
Further, in order to expand the photosensitive wavelength region of these photobase generators, a photosensitizer can be appropriately coexisted. Bases generated by photolysis of these photobase generators act on the base proliferating agent to promote the generation of new bases.
An appropriate amount of auxiliary additives such as inorganic fillers such as silica, talc, and alumina, organic fillers, and pigments can be further added to the photocurable resin composition of the present invention as necessary.
The photo-curable resin composition of the present invention is suitable for coating materials, adhesive materials, and the like.

Next, the present invention will be described in detail by examples.
[Synthesis Example 1 (Synthesis of Siloxane-modified Photobase Generator)]
2-Nitrobenzyl alcohol 3.90 g (25.5 mmol) was placed in a 200 mL four-necked flask equipped with a 100 mL dropping funnel, and 32 mL of Benzene and 0.12 g of Di-n-butyltin dilaurate were added thereto. To the dropping funnel, a solution prepared by dissolving 9.23 g (37.3 mmol) of 3-Isocyanapropyltrioxysilane in 24 mL of Benzen was added.
After being dropped and mixed at 60 ° C. with stirring in a four-necked flask, the reaction solution was stirred at 60 ° C. for 90 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting liquid was purified using column chromatography (filler: silica gel). At that time, the silica gel was washed with developing solvent 1 (Hexane: Ethyl acetate: TEOS = 75: 25: 1), and then purified using developing solvent 2 (Hexane: Ethyl acetate = 3: 1). As a result, 4.96 g (yield 82%) of 2-Nitrobenzoyl3- (3-trioxysilyl) propylcarbamate as a target product was obtained as a pale yellow liquid.

[Synthesis Example 2 (Synthesis of a base-proliferating siloxane resin)]
Ethanol 2.49 g (54.2 mmol) was added to a 200 mL four-necked flask equipped with a stirring rod, and 1.23 g (3.38 mmol) of 3-nitropentan-2-yl-3- (triethoxysilyl) was added thereto. After adding propyl carbamate (II) and stirring in an ice bath for 10 minutes, hydrochloric acid and water were added at a molar ratio of HCl / II = 0.105 and H ₂ O / II = 4.0. Thereafter, the mixture was stirred in an ice bath for 10 minutes and further at room temperature for 10 minutes, and then stirred at 70 ° C. for 2 hours at a nitrogen flow rate of 360 mL / min. The obtained reaction product was dissolved in THF and extracted with hexane to obtain a colorless transparent viscous liquid with a yield of 60%.

[Synthesis Example 3 (Synthesis of Polymer Introduced with Oxirane Group and Photobase Generator)]
In a 200 mL four-necked flask equipped with a stirring rod, 29.8 g (126 mmol) of (3-glycidoxypropyl) trimethoxysilane, 5.6 g (14 mmol) of the siloxane-modified photobase generator synthesized in Synthesis Example 1, and 14 mL of methanol After stirring in an ice bath for 10 minutes, 4.81 g of 6N hydrochloric acid and 2.27 g of water were added, and the mixture was further stirred in an ice bath for 10 minutes and at room temperature for 10 minutes. Thereafter, the mixture was heated in an oil bath at 70 ° C. for 3 hours under a stirring rotational speed of 150 rpm and a nitrogen flow rate of 360 mL / min to conduct a hydrolysis polycondensation reaction. The obtained viscous liquid was diluted with benzene, and extraction was performed using hexane as a precipitating agent to obtain 17.7 g (yield 50%) of a colorless viscous liquid.

<Examples 1-3 and Comparative Examples 1-3>
The following (a)-(c) evaluation was implemented after mixing by the compounding ratio of the following Table 1, and the result was described in Table 1.
(A) Photocuring property evaluation method:
Using a He-Xe lamp, adjusting the height of the light source to be 10 mW / cm ² , determining the tackiness of the surface after heating for 60 minutes at 100 ° C. after exposure for 10 seconds, and Judged to.
○: No tack Δ: Some tack remains ×: Tack remains (b) Hardness evaluation method:
After resin mixing, after applying at 1000 rpm using a spin coater, using a He—Xe lamp, the height of the light source was adjusted to 10 mW / cm ² , exposed for 10 seconds, and then heated at 100 ° C. for 60 minutes. After cooling, the hardness by pencil hardness was measured.
(C) Measuring method of adhesion strength:
After resin mixing, it is applied to a glass plate (JIS-R3202) so as to form a circle with a diameter of 5 mm, and the glass plate (JIS-R3202) is bonded together. Using a He—Xe lamp, the height of the light source was adjusted so as to be 10 mW / cm ^2, and after exposure for 10 seconds, heating was performed at 100 ° C. for 60 minutes. After cooling, the peel strength was measured by Intesco.

Claims (7)

  By light containing at least one substituent selected from an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group and an alkoxybenzyl carbamate group as a substituent of the alkoxysilane A photocurable resin composition comprising a photobase generator (A) for generating a base and an alkoxysilane (B) having a functional group capable of reacting with the generated base.   The photocurable resin composition according to claim 1, wherein (A) and (B) are polymerized to a molecular weight of 500 to 30,000 by condensation polymerization of alkoxysilane.   The photocurable resin composition according to claim 1 or 2, wherein the functional group capable of reacting with the base generated by the light of (B) is an oxirane group.   The base proliferating agent (C) that generates a base by the action of a base is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the total of (A) and (B). The photocurable resin composition according to claim 3. The photocurable resin composition according to claim 4, wherein (C) is a siloxane compound having a substituent represented by (Formula 1).

(In the formula, R ¹ and R ² each represent hydrogen, a substituent or an electron-withdrawing group, at least one of which represents an electron-withdrawing group, and R ³ and R ⁴ each represents hydrogen or a substituent. Z represents an amino group.)   The photocurable resin according to claim 5, wherein (C) and (A) and / or (B) according to claim 1 are polymerized to a molecular weight of 500 to 30,000 by polycondensation of alkoxysilane. Composition. Furthermore, an epoxy resin (D) is contained, The photocurable resin composition in any one of Claims 1-6 characterized by the above-mentioned.